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Transition Metal-Catalyzed
Benzofuran Synthesis
Heterocycle Synthesis Series
Xiao-Feng Wu and Yahui Li

Leibniz-Institut für Katalyse e.V.
an der Universität Rostock (LIKAT),
Rostock, Germany
Elsevier
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The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
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Practitioners and researchers must always rely on their own experience and knowledge in
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Typeset by MPS Limited, Chennai, India
CHAPTER
Introduction
1
Benzofurans is a class of heterocyclic compound consisting of fused
benzene and furan rings. As naturally occurring compounds, benzo-
furans have been used in pharmaceuticals, etc. as well (Scheme 1.1).
Due to their potential applications, numerous methodologies have
been developed during the past few decades for their selective and
effective preparation [1].
In this volume, the progress of transition metal-catalyzed furan

synthesis is discussed. Based on the catalysts applied, this text is
organized by Pd, Cu, Ru, Rh, Pt, etc., i.e., the catalyzed reactions for
the synthesis of benzofuran. Some traditional procedures have been
included and discussed here as well to ensure readability.
CH3 HO
O HO
iPr HO
I OH
N HO
H
C 5H 11
O O
O OH
H 3C
I O
Cannabifuran Amiodarone Malibatol A
MeO OMe OMe

N
HO
R1 OMe OH
O
N O
R2
O O Ailanthoidol Antituberculosis agent
R 1=NH2 or N(Me) 2
R 2=H, Me or OMe
R 1= NH2 , R 2=6-OCH 3
R 1=N(CH3 )2 , R 2 =6-OCH 3
Tubulin polymerization inhibitors
Scheme 1.1 Selected examples of benzofuran derivatives.
Transition Metal-Catalyzed Benzofuran Synthesis. DOI: http://dx.doi.org/10.1016/B978-0-12-809377-1.00001-2

Copyright © 2017 Elsevier Inc. All rights reserved.
2 Transition Metal-Catalyzed Benzofuran Synthesis
REFERENCES
[1] a) Hayta, S. A.; Arisoy, M.; Arpaci, O. T.; Yildiz, I.; Aki, E.; Ozkan, S., et al. Eur. J. Med.
Chem. 2008, 43, 2568 2578.
b) Yeung, K.-S. Heterocycl. Chem. 2012, 29, 47 76.
c) Kamal, M.; Shakya, A. K.; Jawaid, T. Int. J. Med. Pharm. Sci. 2011, 1, 1 15.
d) Verma, A.; Pandeya, S. N.; Sinha, S. Int. J. Res. Ayurveda Pharm. 2011, 2, 1110 1116.
e) Deshpande, R.; Bhagawan Raju, M.; Parameshwar, S.; Shanth Kumar, S. M.;
Appalaraju, S.; Yelagatti, M. S. Am. J. Chem. 2012, 115 120.
f) Lin, S.-Y.; Chen, C.-L.; Lee, Y.-J. J. Org. Chem. 2003, 68, 2968 2971.
g) Zhu, R.; Wei, J.; Shi, Z. Chem. Sci. 2013, 4, 3706 3711.
h) Li, B.; Yue, Z.; Xiang, H.; Lv, L.; Song, S.; Miao, Z., et al. RSC Adv. 2014, 4, 358 364.
CHAPTER 2
Pd-Catalyzed Benzofuran Synthesis
In 1986, Marinelli and coworkers developed a palladium-catalyzed

reaction of o-iodophenols with 1-alkynes. This method represents a
very useful procedure for the synthesis of substituted-benzo[b]furan
(Scheme 2.1) [1]. In this procedure, good yields of the benzo[b]furan
can be obtained in the presence of Pd(OAc)2(PPh3)2 (2 mol%), CuI
(4 mol%), and piperidine at room temperature, or 60 C. This method
also has two main advantages. One is mild reaction conditions, and
the other is compatibility with a variety of functional groups, both in
the phenolic and the alkyne moiety.
Later, Kundu and coworkers reported palladium-catalyzed hetero-

annulation of acetylenic compounds for synthesis of benzo[b]furan
(Scheme 2.2) [2]. They synthesized a number of 2-substituted benzofur-
ans from readily accessible starting materials under relatively mild con-
ditions and with fair to excellent yields. Some of the synthesized
compounds were easily converted to known natural products or com-
pounds of biological interest.
Y Pd(OAc) 2 (PPh3 )2 Y
X CuI, piperidine
+ R R
DMF, 25–60 o C O
OH
X = Br, I
Scheme 2.1 Palladium-catalyzed synthesis of benzo[b]furan from alkynes.
I
PdCl2(PPh)3 , CuI
+ R R
OH Triethylamine, DMF O
Scheme 2.2 Palladium-catalyzed synthesis of benzo[b]furan from alkynes.

Scheme 2.2
Synthesis of benzofuran-2-ylmethanol. A mixture of o-iodophenol
(2 mmol), PdC12(PPh3)2 (0.07 mmol), CuI (0.26 mmol), and triethylamine
(4 mmol) was stirred in dimethylformamide (5 mL) under nitrogen for 1 h.
Prop-2-ynyl alcohol (4 mmol) was added, and the mixture was stirred
at room temperature for 1 h more and heated at 60 C for 16 h. The
mixture was then cooled, poured into water (100 mL), and extracted with
dichloromethane (3 3 50 mL). The combined organic extracts were washed
with 5 mol dm23 sodium hydroxide (3 3 100 mL) and water, dried
(MgSO4), and purified by chromatography on neutral alumina.
R' COOMe
R R
PdI 2 -thiourea
R'
CBr 4, Cs 2 CO 3 O
OH
CO, MeOH, 40 ºC
Scheme 2.3 Palladium 2 thiourea catalyzed carbonylative annulation of o-hydroxylarylacetylenes.
Yang and coworkers developed an effective cocatalysis system

(PdI2-thiourea and CBr4) for carbonylative cyclization of both
electron-rich and electron-deficient o-hydroxylarylacetylenes to the cor-
responding methyl benzo[b]furan-3-carboxylates (Scheme 2.3) [3]. The
application of this cocatalyst system to a silyl linker-based solid-phase
benzo[b]furan-3-carboxylate synthesis proved to be as effective as in
solution phase.
In 2003, the same group reported synthesis of conformationally

restricted 2,3-diarylbenzo[b]furan by the Pd-catalyzed annulation of
o-alkynylphenols (Scheme 2.4) [4]. The reaction used Pd2(dba)3 as the
catalyst, bipyridine as the ligand, and gave the desired results in good
yield. The aryl iodides with electron-withdrawing groups gave the best
results, presumably due to their favorable effect on the oxidative addi-
tion to the Pd0 complex.
Scheme 2.4
General Procedure for the Palladium-Catalyzed Formation of
2,3-Biarylbenzo[b]furans. Pd2(dba)3 (46 mg, 0.05 mmol, 5 mol%) was
added to a solution of acetonitrile (3.0 mL), ArI (2.0 mmol, 200 mol%),
Pd-Catalyzed Benzofuran Synthesis 5
bpy (16 mg, 0.1 mmol, 10 mol%), and K2CO3 (552 mg, 4.0 mmol) and
the mixture was stirred at 50 C for 1 h. To this solution a solution of
o-alkylnylphenol (1.0 mmol, 100 mol%) in acetonitrile (2 mL) was added,
and the reaction mixture was stirred at 50 C for 5 h under Ar2
atmosphere. The reaction mixture was then concentrated, and the residue
was filtered through a silica gel pad and eluted with EtOAc. The filtrate
was concentrated, and the residue was purified by flash chromatography
on silica gel to give the corresponding cyclization product.
R' Ar
R
R
Pd 2(dba) 3 (5 mol%) R'
+ ArI O
bpy (10 mol%)
OH
K2CO 3 , CH 3CN, 50 o C
NO 2
OMe
Ph Ph Ph
O O O
64 % 87 % 74 %
O
Ph Ph
O O 52 %
85 %
Scheme 2.4 Synthesis of 2,3-diarylbenzo[b]furan by the Pd-catalyzed.
The key step of the previous three approaches is attack of a nucleo-

philic phenol oxygen atom onto an activated C C multiple bond. In
2004, Willis et al. reported alternative palladium-catalyzed cyclization
in which the nucleophilic oxygen atom of an enolate was coupled with
a halo-substituted arene ring (Scheme 2.5) [5]. In the presence of
Pd2(dba)3 and the ligand DPEphos, the corresponding benzofurans
were obtained by intramolecular C 2 O bond formation between
1-(2-haloaryl)ketones and aryl halides. Both cyclic and acyclic ketones
are efficient substrates.
R' O R''
R
R Pd 2(dba) 3 (2.5 mol%)
R'' R'
DPEphos(6 mol%) O
Br base(2.2 equiv.), toluene, 110°C
Substrate Product Yield
O O
95%
Br
O
O
94%
Cl
O O
95%
Cl
O O
81%
Br
O O
80%
Br
O O
F 68%
Br
F
O
O N
N
86%
Cl
Scheme 2.5 Palladium-catalyzed intramolecular o-arylation of enolates.
Scheme 2.5
Synthesis of 1,2,3,4-tetrahydro-dibenzofuran. Cesium carbonate (0.18 g,
0.56 mmol) was added to a flask charged with Pd2(dba)3 (9 mg,
0.01 mmol) and DPEphos (13 mg, 0.02 mmol) under nitrogen. The
reagents were suspended in anhydrous toluene (1 mL), 2-(2-bromophenyl)
cyclohexanone (0.10 g, 0.40 mmol) was added, and the reaction was
heated to 100 C for 20 h. After cooling the reaction mixture was filtered
through a plug of celite and the filtrate reduced in vacuo. The residue
was purified via flash chromatography (petroleum ether) to yield the title
compound (64 mg, 95%) as a colorless oil.
In 2004, Pan and coworkers reported the synthesis of

benzofurans in ionic liquid by a PdCl2-catalyzed intramolecular Heck
reaction (Scheme 2.6) [6]. The reaction was carried out in ionic liquid
PdCl2 (5 mol%), (n-Bu) 3N

O R''' O
NH 4O 2CH, (BMIm)BF 4
R' R' R''
R'' R'''' 60ºC, 24 h
I
R''''
R'''
1 2
1 2 Yield
O O
71%
O O
87%
O O
85%
O n-C 7 H 15 O
n-C 7H 15 78%
I
O O
45%
I I
O O
43%
Cl I Cl
Scheme 2.6 Synthesis of benzo[b]furans in ionic liquid by a PdCl2-catalyzed intramolecular Heck reaction.
(1-n-butyl-3-methylimidazolium tetraborate) and substituted-benzo[b]

furans were obtained in modest to satisfactory yields. Interestingly, the
ionic liquid containing Pd catalyst can be used four times with little loss
of activity.
In 2002, Li and coworkers developed palladium-mediated reactions
for the synthesis of all four possible benzo[4,5]-furopyridine tricyclic
heterocycles, benzo[4,5]furo[2,3-b]pyridine, benzo[4,5]furo[2,3-c]pyri-
dine, benzo[4,5]furo[3,2-c]pyridine, and benzo[4,5]-furo[3,2-b]pyridine,
from the simple substances 2-chloro-3-iodopyridine, 3-chloro-4-stannyl-
pyridine, 4-chloro-3-iodopyridine, and 2-chloro-3-hydroxypyridine, respec-
tively (Scheme 2.7) [7].
In 2005, Yamamoto and coworkers developed platinum-olefin-
catalyzed carbo-alkoxylation of alkynylphenyl acetals for the synthesis
of benzo[b]furan (Scheme 2.8) [8]. The reaction was carried out in the
presence of 2 mol% of PtCl2 and 8 mol% of 1,5-cyclooctadiene (COD)
in toluene at 30 C. They also applied the reaction for the synthesis of
vibsanol, which was isolated from Viburnum awabuki. It is well known
that vibsanol works as an inhibitor of lipid peroxidation. They also
provided a possible mechanism for the reaction (Scheme 2.9).
In 2006, Li and coworkers reported a novel and selective
palladium-catalyzed annulation of 2-alkynylphenols method for the
synthesis of 2-substituted 3-halobenzo [b]furans. The method affords
products with a halide (Cl or Br) at the 3 position. Adding a halide at
the 3 position provides a way to introduce new groups for the synthesis
of new products (Scheme 2.10) [9]. Also, under optimized reaction con-
ditions, most halobenzo [b]furans can be obtained in good yield.
More recently, the same group reported PdCl2-promoted electro-
philic annulation of 2-alkynylphenol derivatives with disulfides or dise-
lenides in the presence of iodine (Scheme 2.11) [10]. This method
allows the reactions between 2-alkynylphenol derivatives and disulfides
I
I I
I
N OH N Me 3 Sn-SnMe 3 N
NaH, DMF, reflus, 89% PdCl2 (Ph 3P)2
Cl O O
xylene,reflux,92%
Scheme 2.7 Synthesis of benzo[4,5]furopyridines via palladium-mediated reactions.

R''
R'''
R' 2 mol% PtCl2 O
R''' 8 mol% 1,5-cyclooctadiene

Toluene, 30ºC R'
R'' O
O O
Et Et Et
O O O
(CH 2) 4Cl (CH 2) 5CH 3

O O O
92% 91% 94%

Et Et Et
O O O
O
O O O
trace 90% 88%
Bn
Et Et
O
O O
CF3
O
O O
61% 73% 83%
Scheme 2.8 Synthesis of 2,3-disubstituted benzofurans by platinum-olefin-catalyzed arboalkoxylation of alkynyl-

phenyl acetals.
R'''
OR'' R'
PtCl2
R'
O
O
R''' OR''
Cl2 Pt R'
R'''
Cl2Pt –
OR''
R' O
O
R''' OR''
–
PtCl2
R'
O+
OR''
R'''
Scheme 2.9 Possible mechanism.

R X H
PdX 2/CuX 2
R' R' R + R' R
HEt 3NX
OH O O
DCE, rt
Major Minor
X = Cl, Br
Scheme 2.10 Palladium-catalyzed annulations of 2-alkynylphenols to form 2-substituted 3-halobenzo[b]furans.
R' YR'''
R'''
PdCl 2, I 2
R + Y Y R' R'
R''' MeCN; 80ºC
OR'' O
Y = S, Se
Substrate 1 Disulfide 2 Yield
S 92%
S
OMe
CF 3 S
65%
S
OMe
MeO S
93%
S OMe
OMe
F S
S F 87%
OMe
F
S 60%
S
OMe F
Cl S 77%
S Cl
OMe
Scheme 2.11 PdCl2-catalyzed electrophilic annulation of 2-alkynylphenol derivatives with disulfides or diselenides.
(or diselenides) for the synthesis of 3-chalcogen-benzo[b]furans. The

key step of the reaction is generation of RYI (Y 5 S, Se) in situ from
the reaction of RYYR with I2. PdCl2 can improve the reaction. In the
presence of PdCl2 and I2, a variety of 2-alkynylphenol derivatives
underwent annulation reactions with disulfides or diselenides to
successfully result in corresponding 3-sulfenylbenzofurans and 3-selene-
nylbenzofurans in moderate to excellent yields.
Scheme 2.11
A mixture of 2-alkynylphenol derivative 1 (0.2 mmol), disulfide or disele-
nide 2 (0.1 mmol), I2 (2 equiv.), and PdCl2 (10 mol%) in MeCN (2 mL)
was stirred at 80 C for the indicated time until complete consumption of
starting material as monitored by TLC and GC MS analysis. After the
reaction was finished, the mixture was poured into ethyl acetate, which
was washed with saturated NaS2O3 and extracted with diethyl ether.
The organic layers were dried over anhydrous Na2SO4 and evaporated
under vacuum. The residue was purified by flash column chromatography
(hexane/ethyl acetate) to create the products.
In 2008, Aurrecoechea and coworkers developed a new

Pd-catalyzed tandem intramolecular oxypalladation/Heck-type cou-
pling between 2-alkynylphenols and alkenes, leading to 3-(1-alkenyl)
benzofurans (Scheme 2.12) [11]. In the presence of PdCl2 and KI,
2-alkynylphenols reacted with alkenes, resulting in the desired benzo-
furan with excellent to good yields. The reaction has some features
including (1) a high degree of structural diversity, (2) effective partici-
pation of ketone derivatives without unwanted hydroarylation-type
side reactions, and (3) tolerance of substitution at the electron-deficient
olefin β position.
Scheme 2.12
To a solution of 2-alkynylphenols (0.24 mmol) in DMF (2 mL) was added
PdCl2 (0.003 g, 0.012 mmol), KI (0.020 g, 0.120 mmol) and alkenes
(1.44 mmol) and the mixture was stirred at 80 C for 20 h. The mixture was
allowed to cool to 25 C and water was added. The mixture was extracted
with EtOAc (three times), the combined organic layers were dried
(Na2SO4), and the solvent was removed. The residue was purified by chro-
matography (silica gel, 95:5 hexane/EtOAc) to afford the desired product.
R1 R2
+ alkene PdCl2, KI
DMF, air, 80 oC O
OH
Entry Alkene Product Yield

CO2nBu
O
1 91
O
O
CO2Me
O
2 71
O
O
COMe
O
3 91
O
COMe
O
4 56
O
O
O
5 31
O
O
O
6 36
O
CONH2
O
7 50
NH2
O
Ph
8 57
Scheme 2.12 Palladium-catalyzed cyclization of 2-alkynylphenols and alkenes.

More recently, Sridhar Reddy and coworkers palladium-catalyzed

tandem intramolecular oxy/amino-palladation/isocyanide insertion for
the synthesis of α-benzofuranyl/indolyl-acetamides (Scheme 2.13) [12].
The reaction does not need oxidant or ligand to promote the cascade
and can be carried out in open air. The reaction also includes isocya-
nide insertion.
In 2015, Chen and coworkers reported one-pot synthesis of

2,3-disubstituted dihydro-benzofurans and benzofurans via rhodium,
palladium-catalyzed intramolecular C H insertion reaction
(Scheme 2.14) [13]. The reactions proceeded via rhodium-catalyzed
ring-opening of N-sulfonyl-1,2,3-triazles, the intramolecular Csp3 H
insertion reaction of a-imino rhodium carbene, and subsequent
palladium-catalyzed dehydrogenation. 2,3-Disubstituted hydrobenzo-
furans and benzofurans can be obtained in good to excellent yields in
a one-pot manner.
The formation of 4 appears to proceed via the insertion of a-imino
rhodium carbene toward a C H bond adjacent to oxygen and
subsequent isomerization of the double bond in the presence of a Pd/C
catalyst. However, when the reaction was carried out under N2 atmo-
sphere instead of H2, the isolated 2 was transformed into benzofuranyl
imine 3 rather than 4 in the presence of Pd/C in CH2Cl2 or EtOH.
This indicates that the transformation of 2 4 is not a simple isomeri-
zation process. Similarly, 3 could also be obtained from 1 via the one-
pot, two-step process in N2 atmosphere (Scheme 2.15).
In 2015, Valdes and coworkers reported Pd-catalyzed synthesis of

benzo[b] fused carbo- and heterocycles through carbine migratory
insertion (Scheme 2.16) [14]. This method is an original approach to
substituted benzofurans, which are constructed by the formation of
two C C bonds on the same carbon atom. However, the yield of this
reaction is low.
In 2016, Jiang and coworkers developed palladium-catalyzed
cascade annulation/arylthiolation reaction in order to create functiona-
lized 3-sulfenylbenzofuran derivatives in moderate to good yields
from readily available 2-alkynylphenols and 2-alkynylamines in ionic
liquids (Scheme 2.17) [15]. This protocol provides a valuable synthetic
tool for the assembly of a wide range of 3-sulfenylbenzofuran deriva-
tives. Another feature of this method is the employment of ionic
liquids under mild reaction conditions.
HO R R O R'''
5 mol% PdCl2
2 equiv. Na2 CO3 NH
R'' R''
2 equiv. R'''NC, MeCN
OH O
open air, rt
Entry Product Yield
t
O Bu
1 NH 85%
t
O Bu
2 NH 82%
t
O Bu
Br NH
3 74%
O
t
O Bu
O 2N NH
4 82%
t
O Bu
5 NH 52%
MeO O
Ph O tBu
6 NH 78%
t
Ph O Bu
7 NH 75%
t
O Bu
O 2N NH
8 81%
Scheme 2.13 Synthesis of α-benzofuranylacetamides via oxypalladation and isocyanide insertion.

N N
N Ts 1) Rh2 (S-PTV) 4 (1 mol%) NHTs
R''
CH2 Cl2, 90 o C, 2h R''
R'
O R' 2) Pd/C (5 mol%), H 2 (1 atm) O
45ºC.3 h
Entry Product Yield
NHTs
1 90%
O
NHTs
2 91%
O
NHTs
3 88%
O
NHTs
4 68%
Cl
O
NHTs Cl
5 76%
O
NHTs F
6 81%
O
NHTs CF3
7 82%
O
NHTs OMe
8 70%
NHTs
9 OMe 57%
O
Scheme 2.14 One-pot synthesis of benzofurans.

N N TsN NTs
N Ts Rh
Rh 2(L) 4 H - Rh 1,3 H shift
R
O R O R O
H
1 A B
Ts
NHTs N NTs N
H
Pd H -H2 Ts
Pd/C, H2
R R R
R O
O O O
C 3 4
2
Scheme 2.15 Possible mechanism.
Ar
R I NNHTs R
Pd 2(dba) 3 , Sphos
+
Ar H t-BuOLi , 5 equiv. H2 O
O O
CH3 CN, 85ºC
R Ar Yield
H 4-Me 2N-C 6 H4 50%

H 4-MeO-C 6H 4 77%
H Ph 60%
H 4-F-C 6 H 4 57%
H 4-Me-C 6H 4 59%
H 3-Cl-C 6H 4 58%
H 4-CF3 -C 6 H4 68%
H 4-CN-C 6H 4 73%
H 2-Furyl 40%
MeO Ph 68%
Scheme 2.16 Palladium-catalyzed synthesis of benzofurans.
Scheme 2.17
Pd(TFA)2 (5 mol%) and [Bmim]Cl (1 mL) were combined in an Schlenk
tube equipped with a stir-bar and stirred at room temperature for 10 min.
A balloon filled with N2 was connected to the Schlenk tube via the
side tube and purged three times. Then, 2-alkynylphenols (0.20 mmol),
arylboronic acid (0.4 mmol), S8 (0.60 mmol), CuI (0.40 mmol), Phen
(0.44 mmol), Ag2CO3 (0.4 mmol), and K3PO4 (0.4 mmol) were quickly
added to the tube under N2 atmosphere and stirred at 80 C for 8 h. After
the reaction was completed, the N2 gas was released carefully, and the
reaction was quenched by water and extracted with CH2Cl2 three times.
The combined organic layers were dried over anhydrous Na2SO4 and
evaporated under vacuum. The desired products were obtained in the cor-
responding yields after purification by flash chromatography on silica gel
with hexanes/ethyl acetate.
R'' Pd(TFA) 2 (5 mol%), CuI (1 equiv.) S Ar

Phen (1.1 equiv.)
R' + ArB(OH) 2 + S8 R''
K3 PO4 (2 equiv.), Ag2CO3 (2 equiv.) R'
OH O
(Bmim)Cl (1 mL), N 2 , 80ºC
Entry Product Yield
SPh
1 78%
n
Pr
O
SPh
2 75%
Et
O
SPh
3 S 68%
O
SPh
4 74%
O
Cl
SPh
5 93%
O
SPh
6 80%
F O
Scheme 2.17 Palladium-catalyzed synthesis of 3-sulfenylbenzofurans.

R'' R''
R'''
Pd/C (5 mol% Pd)
R' R' R''' + H 2
H N 2 , DMA, 140ºC
OH O
1 2
D
Pd(0) HPd(II)H
A H2 C
R'' R''
PdH
R''' B R'''
R' R'
O PdH O H
3 4
Scheme 2.18 Palladium-catalyzed synthesis of benzofurans and proposed mechanism.
In 2016, Liu and coworkers reported palladium-catalyzed C H

functionalization of ortho-alkenylphenols for the synthesis of substi-
tuted benzofurans. The reaction used palladium on carbon (Pd/C) as
the catalyst and did not require any oxidants or sacrifice of hydrogen
acceptors (Scheme 2.18) [16]. The reaction also has good tolerance of
different functional groups under optimized coupling conditions.
Ethers, aryl fluorides, carboxylic esters, trifluoromethylbenzenes,
nitriles, and naphthalene also proved compatible. The researchers also
provided an overall mechanism for this catalytic dehydrogenative cou-
pling reaction. In their opinion, the reaction mechanism is formally
similar to a Heck reaction mechanism. The reaction begins with an
oxidative addition in which palladium inserts itself in the O H bond
to form the organopalladium intermediate 3. A similar process in
which palladium (0) inserts itself into O H bonds has been observed
in oxidant- and acceptor-free dehydrogenation of alcohols. Then the
double bond inserts itself in the palladium-oxygen bond in a syn addi-
tion step to generate 4. The intermediate 4 is then converted into the
target compound by a β-hydride elimination step with the formation of
HPdH. The palladium(0) compound is regenerated by reductive elimi-
nation of the HPd(II)H with H2.
In 2016, Zhou and coworkers reported the synthesis of (Z)-α-tri-

fluoromethyl alkenyl triflates and their applications in a straightfor-
ward synthesis of trifluoromethylated benzofurans (Scheme 2.19) [17].
CF3
CF3 1) KHCO3 (2.0 equiv.), DMF, 30ºC
R
OTf 2) 2-IC 6 H 4OH (1.2 equiv.), Pd 2(dba)3 (10 mol%), R
O
(t-Bu) 3 P (0.8 equiv.), K 2 CO3 (5.0 equiv.), DMF,
140ºC
Entry Product Yield
CF3
1 60%
O
CF3
2 61%
O
Cl
CF3
3 50%
O
OMe
CF3
4 61%
Ph
O
Scheme 2.19 Synthesis of 3-trifluoromethylbenzofuran.
The reaction used Pd(OAc)2 as the catalyst, X-Phos as the ligand, and
Cs2CO3 as the base. Their method can also be used for the synthesis of
3-trifluoromethylbenzofuran, which is an essential structural motif in
biologically active compounds.
In 2011, Li and coworkers reported palladium-catalyzed selective

heck-type diarylation of allylic esters with aryl halides. This methodology
can also be applied in constructing the indole and benzofuran skeletons
(Scheme 2.20) [18]. Both 2-iodophenol and 2-bromophenol are
also suitable substrates, providing the desired benzofuran in satisfactory
yields.
In 1998, Bumagin and coworkers developed Pd21-catalyzed

oxidative cyclization of 2-allylphenols for synthesis of benzofurans
(Scheme 2.21) [19]. Oxidative cyclization of 2-allylphenols can be
performed easily and under mild conditions using palladium dichloride
as a catalyst, Cu(OAc)2 LiCl as a reoxidant, and aqueous
OH O
R PdCl2
OY +
X n-Bu 4 NCl, K 2 CO3 R
R' R'
X = I, Br DMA, 100ºC
1 2
1 2 Product
OH
OAc
I O 71%
OH
OAc
Br O
52%
Scheme 2.20 Palladium-catalyzed synthesis of benzofuran.
2 mol% PdCl 2, Cu(OAc) 2, LiCl

R R
OH DMF-H 2O, RT O
Scheme 2.21 Synthesis of benzofurans via Pd21-catalyzed oxidative cyclization of 2-allylphenols.
dimetyl-formamide as a solvent. A number of functionalized 2-methyl-

bezofurans were obtained in high yields.
In 2010, Correia and coworkers developed an intramolecular
Heck Matsuda reaction and applied it in the syntheses of benzofurans
and indoles (Scheme 2.22) [20]. The reaction has a wide scope of sub-
strates. Both electron-donating and/or electron-withdrawing groups at
the aromatic position can be tolerated. However, electron-rich, -poor
and -neutral substituents resulted in Heck adducts in lower yields,
compared to those obtained for an unsubstituted benzofuran.
In 2011, Lu and coworkers reported the synthesis of 1-benzoxepine
derivatives via cationic palladium-catalyzed [5 1 2] annulation reaction
of 2-acylmethoxyarylboronic acids with allenoates (Scheme 2.23) [21].
This annulation involves the intramolecular nucleophilic addition to
ketones without the formation of π-allylpalladium species.
In 2015, Stahl and coworkers reported a palladium-catalyzed

aerobic oxidative dehydrogenation system that can be used for synthe-
sis of benzofurans (Scheme 2.24) [22]. The reaction used O2 as the
O Pd(OAc) 2 (5 mol%) O
R
N 2BF4 MeOH, 50ºC
Entry Substrate Product
O O
1
N 2BF4
30%
O O
2
MeO N 2BF4 MeO

31%
O O
3
Cl N 2BF4 Cl
trace
Scheme 2.22 Synthesis of benzofurans via Pd21-catalyzed cyclization of the aryl o-allylether.
B(OH) 2
(Pd(dppp)(H 2 O) 2) 2+(TfO -) 2
+
O CO2Et dioxane, 0.5h, 80ºC O
O 73%
Scheme 2.23 Synthesis of benzofurans via annulation reaction of the 2-formylphenylboronic acids with substituted
allenoates.
oxidant, which enables efficient synthesis of substituted arene deriva-

tives and shows good functional group tolerance.
In 2011, Sanz and coworkers reported a Pd-catalyzed Buchwald

protocol in an attempt to synthesize the desired dimethoxybenzo[b]
furan derivatives (Scheme 2.25) [23]. The reaction of the previously
prepared o-haloaryl alkynes with KOH, in the presence of catalytic
amounts of Pd2(dba)3 and t-BuXPhos at 100 C in a 1:1 mixture of
H2O:1,4-dioxane, gave rise to the corresponding benzo[b]furan deriva-
tives in moderate to good yields.
In 2013, Chen and coworkers developed a new synthesis of 2-aryl-

benzofurans by palladium-catalyzed reaction of arylboronic acid with
5% Pd(OAc) 2 /25 % pTsOH

20% AMS
MgSO 4, PhCl 1M
24h, 110ºC, O2
Substrate Product Yield(conv.)
31(34)
53(61)
62(100)
O O
Scheme 2.24 Synthesis of benzofurans via annulation reaction of the 2-formylphenylboronic acids with substituted
allenoates.
OMe R OMe
Pd2 (dba) 3 (2 mol%)
t-BuXPhos (8 mol%)
+ KOH R
X H 2 O/1,4-dioxane(1/1) O
MeO MeO
C: 100ºC, 12–24 h
D: MW (150ºC), 12 min 50–81%
Scheme 2.25 Synthesis of benzofurans.
aliphatic nitriles (Scheme 2.26) [24]. The reactions used Pd(OAc)2

(5 mol%) as the catalyst, bpy (10 mol%) as the ligand, TFA as the
additive, and THF-H2O as the solvent. The electronic properties of the
groups on the phenyl ring of the benzoboronic acid had some effect on
the yield of the reaction. Arylboronic acids, which have electron-
donating groups at the para position, have higher yield.
In 2013, the same group also developed a new method for synthesis
of benzofurans from potassium aryltrifluoroborates and hydroxyphe-
nylacetonitriles (Scheme 2.27) [25]. The reaction used Pd(CF3CO2)2 as
the catalyst, bpy (10 mol%) as the ligand, TFA (10 equiv.) as the addi-
tive, and THF-H2O as the solvent.
CN Pd(OAc) 2 (5 mol%)
ArB(OH) 2 + R R Ar
OH bpy,TFA, THF-H 2O, O
N 2, 80 o C
Entry R Ar Yield[b] (%)
1 H Ph 94
2 H 4-MeC6H4 91
3 H 4-MeOC6H4 92
4 H 4-FC6H4 86
5 H 4-ClC6H4 84
6 H 4-BrC6H4 81
H
7 4-PhC6H4 85
4-Me
8 Ph 91
3-MeO
9 Ph 89
4-Cl
10 Ph 81
4-Br
11 Ph 80
Scheme 2.26 Palladium-catalyzed synthesis of 2-arylbenzofurans.
In 2010, Manabe and coworkers reported palladium-catalyzed synthesis

of bentofuran from 2-chlorophenols (Scheme 2.28) [26]. This method used
a bifunctional ligand L1 for cross-coupling of chloroarenes, and provided a
new example of benzofuran synthesis from 2-chlorophenol.
In 2008, Burch and coworkers developed a palladium-catalyzed
one-pot synthesis of benzofuran from o-bromophenols (Scheme 2.29) [27].
The reaction used Pd(OAc)2 as the catalyst, rac-DTBPB as the ligand,
and NaOtBu as the additive. Then, treatment of the reaction mixture
with a 1:1 mixture of CH2Cl2 and trifluoroacetic acid provided the
benzofurans.
In 2008, Li and coworkers developed a palladium/copper cocata-
lyzed cross-coupling reaction of terminal alkynes with (E)-2,3-diio-
doalkenes for the synthesis of benzofuran (Scheme 2.30) [28]. The
reaction used Pd(OAc)2 and CuI as the catalyst, Et3N as the base, and
THF as the solvent.
CN Pd(OAc) 2 (5 mol%)
ArBF 3K + R R Ar
OH bpy,TFA, THF-H 2O, O
N 2, 80ºC
t-Bu
O O O
97% 92% 95%
OMe Ph
O O O
79% 89% 96%
Cl
F Cl
O O O
88% 75% 85%
Cl
Br I
O O O
76% 68% 73%
Cl Br Br
t-Bu t-Bu
O O O
72% 67% 64%
t-Bu Cl
O O O
91% 91% 81%
Scheme 2.27 Synthesis of benzofurans from the potassium aryltrifluoroborates to 2-hydroxyphenylacetonitriles.
Cl PdCl2(CH 3CN)2 (2 mol%)

R' + R R Ar
L (4 mol%), t-BuOLi (3.6 equiv.),
OH O
t-BuOH, 110ºC
MeO Ph F N
C 10H21 OMe
O O O
42% 78% 79%
Cl
Cl
C10H 21 C 10H21 OMe
O O O
61% 88% 34%
PCy 2 HO
L1
Scheme 2.28 Benzofuran synthesis from 2-chlorophenols and alkyne.

1. Pd(OAc) 2 (5 mol%)
Ligand (10 mol%)
NaO tBu (2.7 equiv.) R1
O
Br
toluene, 80ºC
+ R1 R2
OH 2. TFA/CH 2Cl 2, 23ºC O
R2
Entry Substrate Product Yield [%]
O
1 76
O
2 59
O
O
3 73
O
O O
O
4 65
O
O O
5 84
O
S O S
6 70
O
7 41
O
O
8 75
O
9 84
O
Scheme 2.29 One-pot synthesis of benzofurans.

THF as the solvent.
Pd(OAc) 2 (1 mol%)
OH I R1 O
CuI (5 mol%)
R + R R1
I THF/Et3 N (4:1)
r.t., 18 h, reflux, 18 - 36 h
1 2
R 1 = Ar, Alkyl, CO2 Et
Entry 1 2 Yield (%)
I CO 2Et
1 33
OH I
I Ph
2 63
OH I
I
3 OH 58
OH I
O 2N I Ph
4 91
OH I
OHC
I Ph
5 36
OH I
OMe
Cl nC
I 8H 17
6 57
OH I
Cl
Scheme 2.30 One-pot synthesis of 2-ethynylbenzofurans.
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CHAPTER 3
Cu-Catalyzed Benzofuran Synthesis
In 2005, Chen and coworker reported a CuI-catalyzed ring closure

of 2-haloaromatic ketones for the synthesis of benzo[b]furan
(Scheme 3.1) [1]. The catalyzed protocol can tolerate various functional
R1 R1
R2
CuI(10 mol%), K3PO4 (1.5 eq.)
R2
O DMF,105oC
X O
1 X = I, Br
Entry 1 Product Yield
EtO2C CO2Et
1 88
O O
Br
CN CN
2 91
O O
Br
Br Br
3 93
O O
Br
Cl
Cl
4 92
H
H
O O
Br
OMe
99
5 OMe
O
O
I
Scheme 3.1 Synthesis of benzo[b]furans via CuI-catalyzed ring closure.

groups. The researchers also suggested the reaction occurs through the
intramolecular SRN1 mechanism.
In 2006, SanMartin and coworker reported copper-catalyzed syn-

thesis of benzo[b]-furan derivatives in water (Scheme 3.2) [2]. The reac-
tion involved a copper TMEDA complex and used ketone derivatives
as the starting substances. One of the advantages of this reaction is
O CuI (8 mol%), TMEDA (3.5 eq.) O

R2 R2 R1
R1 H2O,120oC
Br
Entry Starting substance Product Yield (%)

O O
1 76
Br
O O
2 91
Br Cl
Cl
O O
3 99
Br NH2
NH2
F
F O F
O
4 82
F
Br Cl
Cl
O O F
5 74
F
Br
OMe
OMe O OMe
O
6 21
OMe
Br
O
O
7 MeO 83
78 (2nd run)
Br
MeO
Scheme 3.2 Copper-catalyzed straightforward synthesis of benzo[b]furan derivatives in neat water.

Cu-Catalyzed Benzofuran Synthesis 31
using water as the solvent. The benefits of using water are clear in
terms of lack of toxicity, safety, and cost.
Scheme 3.2
A schlenk tube was charged with deoxybenzoin (0.16 mmol), CuI
(2.6 mg, 0.0136 mmol), TMEDA (85 µL, 0.56 mmol), and water
(1.9 mL). Then the tube was sealed under a positive pressure of argon
and the obtained green solution was heated overnight at 120 C. The
product was extracted from the aqueous layer with dichloromethane
(3 3 5 mL), dried, and concentrated in vacuo. The crude mixture was
then purified by flash chromatography (40% hexane/CH2Cl2) to create
benzofuran.
In 2007, Lautens and coworker developed a general method of benzo-

furan synthesis via Cu- and Pd-catalyzed cross-coupling (Scheme 3.3) [3].
R3
R3
Br Pd-C, CuI
P(p-MeOPh)3
R1 + R R1 R
Br
X iPr2NH, PhMe X
100oC
1 R2 2 3 R2
Entry Alkyne Product/yield (%)
1 C6H13 80
2 TMS 47
3 OH 49
4 OTBDPS 80
5 63
OH
6 CN 76
7 71
8 61
N
Scheme 3.3 Copper-catalyzed straightforward synthesis of benzo[b]furan derivatives in neat water.

The reaction used Pd/C- and CuI as the catalyst and used gem-
dibromovinyl substrates and terminal alkynes as the substances. Both
gem-dibromovinyl substrates and terminal alkynes showed good tolerance
on different groups.
Scheme 3.3
A carousel reaction tube (24 3 150 mm) was charged with 1 (0.41 mmol),
10% Pd-C (4.4 mg, 0.0041 mmol, 1 mol%), P(p-MeOPh)3 (5.8 mg,
0.017 mmol, 4 mol%), and CuI (1.6 mg, 0.0083 mmol, 2 mol%), and was
evacuated and purged with argon three times. Toluene (2 mL, degassed),
H2O (1 mL, degassed), iPr2NH (145 µL, 1.03 mmol), and 2 (0.75 mmol) were
added to this mixture and then heated to 100 C with stirring for 12 h. The
reaction mixture was then cooled to room temperature and H2O (10 mL)
added. The mixture was extracted with Ethyl acetate (EtOAc) (2 3 15 mL)
and combined extracts were washed with salt. NH4Cl and brine, then dried,
and solvent was removed in vacuo. The resulting crude material was purified
by flash chromatography eluting with 2% EtOAc in hexane to create the
product.
In 2009, Lautens and coworker reported intramolecular cross-

coupling of gem- dibromoolefins for synthesis of 2-bromo-
benzofused heterocycles (Scheme 3.4) [4]. Highly useful halogenated
benzofurans are prepared from gem-dibromoolefins using a mild,
ligand-free copper catalyzed cross-coupling procedure. In this process
purification by flash chromatography is unnecessary, making this
method highly efficient.
Scheme 3.4
A 0.5 2 mL microwave-reaction vial equipped with a magnetic stir bar
was added to the requisite gem-dibromoolefin (1 eq.), CuI (5 mol%), and
K3PO4 (2 eq.). The flask was flushed with argon for 5 min, after which
THF (1 mL per 0.2 mmol olefin) was added and the vial sealed and
placed in a preheated oil bath at 80 C. The vial was stirred for 6 h, after
which it was removed from the oil bath and allowed to cool to room tem-
perature. The contents were filtered over a pad of silica gel and washed
with copious amounts of Et2O. The resulting solution was concentrated
under reduced pressure to create a spectroscopically pure product.
Br CuI (5 mol%)
K3PO4
R1 R1 Br
Br
THF,100oC O
OH
1 2
Entry Substrate Product Product/yield (%)
Br
1 93
Br Br
OH O
Br
2 Br 95
Br
OH O
OMe MeO
Br
3 89
Br Br
OH O
Br
4 Br 89
Br
MeO OH O
MeO
MeO2C Br MeO2C
5 Br 93
Br O
OH
Cl Br Cl
6 Br 99
Br
OH O
Scheme 3.4 Synthesis of benzofurans by intramolecular Ullmann coupling.
In 2012, Wang and coworker developed a highly efficient one-

pot procedure by reaction of 2-(gem-dibromovinyl)phenols-(thiophe-
nols) with K4Fe(CN)6 to 2-cyanobenzofurans(thiophenes) (Scheme
3.5) [5]. In the presence of CuI/Na2CO3 Pd(OAc)2/PPh3 in N,N-
dimethylformamide (DMF), the reaction of 2-(gem-dibromovinyl)
phenols and 2-(gem-dibromovinyl)thiophenols with K4Fe(CN)6, as a
nontoxic and user-friendly cyanating reagent, generated the corre-
sponding 2-cyanobenzofurans with good yields.
Br 1. CuI (5 mol%)
Na2CO3(2 eq.), DMF
R R CN
Br 2. K4Fe(CN)6 (0.2 eq.) O
OH
Pd(OAc)2/PPh3 (0.5 mol%)
1 2
CN CN
O O CN
O
91% 86% 85%
MeO Cl
O2 N
CN CN
O O CN
O
82% 79% 67%
CN CN
O O CN
MeO O
76% 79% 69%
CN CN
O O CN
O
OMe
OEt
75% 77% 71%
Cl
CN CN
O O CN
O
82% 75% Cl 85%
Scheme 3.5 Cu/Pd-catalyzed one-pot reactions of 2-(gem-dibromovinyl)phenols(thiophenols) with K4Fe(CN)6.
Scheme 3.5
A sealable reaction tube equipped with a magnetic stirrer bar was
charged with gem-dibromovinyl substrate (1.0 mmol), CuI (0.10 mmol),
Na2CO3 (2.0 mmol), and DMF (2.0 mL). The rubber septum was then
replaced by a Teflon-coated screw cap, and the reaction vessel placed in
an oil bath at 80 C. After stirring of the mixture at this temperature for
6 h, it was cooled to room temperature and K4Fe(CN)6 (0.20 mmol), Pd
(OAc)2 (0.01 mmol), and PPh3 (0.02 mmol) were added to the reaction
system. Then the reaction vessel was placed in an oil bath at 120 C for
6 h. It was cooled to room temperature after the reaction and diluted
with ethyl acetate, washed with water and brine, and dried with Mg2SO4.
After the solvent was removed under reduced pressure, the residue was
purified by column chromatography on silica gel (eluant: petroleum
ether) to create the corresponding product.
In 2013, Wang and coworker developed trace amount Cu (ppm)-

catalyzed intramolecular cyclization of 2-(gem-dibromovinyl)-phenols
(thiophenols) to 2-bromo-benzofurans (thiophenes) (Scheme 3.6) [6].
2-bromobenzofurans (thiophenes) can be obtained in the presence of a
X
Cs2CO3(0.5 eq.)
R R X
X C2H5OH, 80oC, 8 h O
OH
If necessary,
X=Br, Cl CuI(25 ppm) was added
Br Br Br
O O O
95% 96% 95%
Cl
Br Br Br
MeO O O O
94% 97%
OMe 92%
Br Cl Br
Br Br Br
O O O
99% 98%
Cl Br 99%
Cl Br
Br Br Br
O O O
Br 99%
94% OMe 90%
O 2N
Br Cl
O Br O
85% O
94% 81%
Scheme 3.6 Trace amount Cu (ppm)-catalyzed intramolecular cyclization for synthesis of 2-bromobenzofurans.
trace amount of Cu (0.0064 mol%, 25 ppm). The reaction provides the

desired products in excellent yields under fluoride-free and mild reac-
tion conditions and with a TON (turnover number) of up to 1.5 3 104.
They also found that the 47 ppm of Cu in the commercially available
Cs2CO3 (99.9% from Shanghai, China) was capable of catalyzing the
intramolecular cyclization of substrates. The reactions were also com-
pleted using Cs2CO3 (99.995% from Aldrich) with additional CuI
(25 ppm), providing comparable yields of products. This method can
also be used in the synthesis of 2-chlorobenzofurans and is a mild and
environmentally-friendly reaction.
Scheme 3.6
A sealable reaction tube equipped with a magnetic stirrer bar was
charged with gem-dibromovinyl substrate (1.0 mmol), Cs2CO3 (99.9%
from Shanghai, 0.50 mmol), and C2H5OH (2.0 mL). The rubber septum
was then replaced by a Teflon-coated screw cap, and the reaction vessel
placed in an oil bath at 80 C. After stirring the mixture at this tempera-
ture for 8 h, it was cooled to room temperature and diluted with ethyl
acetate, washed with water and brine, and dried over MgSO4. After the
solvent was removed under reduced pressure, the residue was purified by
column chromatography on silica gel (eluant: petroleum ether) to create
the corresponding product.
In 2013, Wang and coworker reported a copper-catalyzed decarbox-

ylative intramolecular C O coupling reaction for synthesis of 2-aryl-
benzofuran from 3-arylcoumarin (Scheme 3.7) [7]. The products of
these reactions—2-arylbenzo furans—represent a broad range
of biological activities with significant pharmacological potential. The
starting substances are abundant in nature and can be easily synthe-
sized. Thus this method provides novel and easy access to a variety of
2-arylbenzofurans.
Scheme 3.7
A 25 mL flask was charged with 3-arylcoumarin (1 mmol), cupric chlo-
ride (0.15 mmol), phenathroline (0.15 mmol), DMSO (10 mL), and 4 Å
molecular sieves (300 mg). The reaction mixture was stirred and primarily
R1 Phenyl R1
CuCl2(15 mol%), Phen(15 mol%)
Phenyl
NaOH(3 eq.), MS, air, 150oC O
O O
R2 R2
OCH3 OCH3
OCH3 OCH3
O O O
OCH3 36% OCH3 34% OCH3 41%
Cl F NO2
O O O
OCH3 42% OCH3 36% OCH3 45%

OCH3 H3CO
Cl Cl Cl
OCH3 OCH3
O O O
76% 72% 63%
OCH3
Cl Cl H3CO
OCH3 Cl
OCH3
O O
O
Cl 82% Cl 73% 60%
Cl
OCH3
OCH3
OCH3 OCH3
O O O
47% 52% 56%
Scheme 3.7 Synthesis of 2-arylbenzofuran from 3-arylcoumarin.
heated to 110 C for 1 h and the color gradually turned to dark brown.
The temperature was then raised to 150 C and maintained for 24 h. The
mixture was exposed to air during the reaction time. After cooling to
room temperature, hydrochloric acid (2 mol/L, 10 mL) and water
(20 mL) were added to terminate the reaction, which simultaneously
brought about the generation of brown solid and bubble. The suspension
was then extracted with chloroform (20 mL 3). The combined organic
layer was washed in turn with water (20 mL) and then brine (20 mL),
dried over anhydrous magnesium sulfate, filtered, and concentrated under
reduced pressure. The solid residue obtained was purified by silica gel col-
umn chromatography.
O R1 Rh2(Oct)4(1 mol%)
CuTc(10 mol%) O
R1
O2balloon, toulene
N Ts 100oC, 4 Å MS
1 N N 2 NTs
F
O O O
OMe
NTs NTs NTs

84% 49% 51%
Br CF3
O O O
CO2Me
NTs NTs NTs

65% 41% 74%
O O O
CN
NTs NTs NTs

51% 64% 59%
Scheme 3.8 Synthesis of benzofurans via transition metal-catalyzed tandem intramolecular C(sp3) H insertion.
In 2015, Kang and coworker developed a synthesis of benzofurans

via the transition metal-catalyzed tandem intramolecular C(sp3) H
insertion of azavinyl carbenes, derived from 1-sulfonyl-1,2,3-triazoles
and aerobic oxidation via sequential catalysis (Scheme 3.8) [8]. The
reaction has good tolerance to different groups. Substrates with elec-
tron withdrawing or electron-donating substituents on different posi-
tions of the phenyl ring are also converted to the desired products with
moderate to good yields.
Scheme 3.8
Triazole derivative 1 (0.3 mmol), 4 Å MS (20 mg), CuTc (0.03 mmol,
0.1 eq.), and Rh2(Oct)4 (0.003 mmol,0.01 eq.) were added to an oven-
dried Schlenk tube equipped with a stir bar. The reaction vessel was
evacuated and backfilled with O2 three times before adding freshly dis-
tilled toluene (6.0 mL, 0.05 M). The reaction mixture was stirred under
an O2 (balloon) atmosphere at 100 C (checked by thin layer chromatog-
raphy (TLC)). The residue was purified by flash column chromatography
with ethyl acetate and petroleum ether as eluents to afford 2.
In 2006, Ackermann and coworker also developed copper-catalyzed

benzo[b]furan synthesis (Scheme 3.9) [9]. Aryl chlorides can also be
used in this reaction.
In 2011, Wang and coworker developed a copper-catalyzed cou-

pling reaction for synthesis of benzofurans and indoles (Scheme 3.10)
[10]. The reaction used CuBr as the catalyst, Cs2CO3 as the base, and
MeCN as the solvent. The reaction also has a wide scope of starting
substances. Substrates with electron-withdrawing or electron-
donating substituents on different positions of the phenyl ring can be
tolerated and converted to the desired products with moderate to
good yields.
R2 CuI (10 mol%), L (30 mol%)

K3PO4(1.4 eq.)
R1 R1 R2
O DMF, 105oC, 22 h O
X
Entry Starting substance L Product Yield (%)

nHex
1 – nHex 82
O O
Br
nBu
2 – nBu 82
O O
Br
nHex
3 – nHex 80
O N O
N Br
nHex
4 – nHex 56
O O
N Cl N
F3C nHex F3C
5 Me2NCH2CO2H nHex 69
O
Cl O
Scheme 3.9 Copper-catalyzed benzofuran synthesis.

NNHTs CuBr, Cs2CO3

R1 R2 R1
+
OH MeCN, 100oC O R2
1 2 3
Yield
Entry 1 2 3
(%)
NNHTs
1 O 85
OH
NNHTs O
2 F 70
OH
F
NNHTs O
3 F3C 86
OH
CF3
NNHTs
4 n-C 4H 9 55
OH O n-C4H9
NNHTs
5 MeO O 79
MeO OH
NNHTs
O
6 72
OH OMe
OMe
F
Br
Br
NNHTs
7 O 79
OH
O 2N
O2N
NNHTs
8 O 48
OH
9 NNHTs 53
OH O
Scheme 3.10 Cu-catalyzed reaction of N-tosylhydrazone and various terminal alkynes.

REFERENCES
[1] Chen, C.-Y.; Dormer, P. G. J. Org. Chem. 2005, 70, 6964 6967.
[2] Carril, M.; SanMartin, R.; Tellitu, I.; Domínguez, E. Org. Lett. 2006, 8, 1467 1470.
[3] Nagamochi, M.; Fang, Y.-Q.; Lautens, M. Org. Lett. 2007, 9, 2955 2958.
[4] Newman, S. G.; Aureggi, V.; Bryan, C. S.; Lautens, M. Chem. Commun. 2009, 5236 5238.
[5] Zhou, W.; Chen, W.; Wang, L. Org. Biomol. Chem. 2012, 10, 4172 4178.
[6] Ji, Y.; Li, P.; Zhang, X.; Wang, L. Org. Biomol. Chem. 2013, 11, 4095 4101.
[7] Pu, W.-C.; Mu, G.-M.; Zhang, G.-L.; Wang, C. RSC Adv 2014, 4, 903 906.
[8] Li, L.; Xia, X.-H.; Wang, Y.; Bora, P. P.; Kang, Q. Adv. Synth. Catal. 2015, 357,
2089 2097.
[9] Ackermann, L.; Kaspar, L. T. J. Org. Chem. 2007, 72, 6149 6153.
[10] Zhou, L.; Shi, Y.; Xiao, Q.; Liu, Y.; Ye, F.; Zhang, Y., et al. Org. Lett. 2011, 13, 968 971.
CHAPTER 4
Other Transition Metal-Catalyzed
In 2004 Wang and coworker reported a versatile and new method for the
synthesis of benzofurans from various phenols by the following strategy:
(1) various allyl phenyl ethers (2a-f) prepared from O-alkylation of
various phenols (1a-f) with corresponding alkyl halide underwent [3,3]
sigmatropic (Claisen) rearrangement to furnish O-allylphenols (3a-f),
respectively; (2) then, (3a-f) underwent O-chloroethylation with an excess
of 1,2-dichloroethane, sodium hydroxide in water, and terabutylammo-
nium bromide as phase catalyst to give monoalkylated products (4a-f);
(3) treatment of compound 4a-f with potassium tertbutoxide in THF
underwent isomerization of the allyl group together with 1,2-elimination
of O-(2-chloroethyl) group to build up the O-vinyl and C-propenyl func-
tion as precursor (5a-f) for RCM; (4) finally, the cyclization of compound
5a-f with Grubbs’ catalyst underwent RCM to create various benzofurans
(6a-f) with good overall yields (Scheme 4.1) [1].
In 1998 Furukawa and coworker developed Ru and Cu cocatalyzed
cyclization of 2-allylphenol to 2,3-dihydro-2-methylbenzofuran without
β-elimination (Scheme 4.2) [2]. The intramolecular nuclephilic addition
of 2-allylphenol was catalyzed by RuCl3/AgOTf-PPh3-Cu(OTf)2 to
afford 2,3-dihydro-2-methylbenzofuran with good yields.
In 2009 Hashmi and coworker reported a gold-catalyzed reaction

for synthesis of benzo[b]furans. The mono-substituted furans could be
converted to benzo[b]furans with low yields (Scheme 4.3) [3]. The reac-
tions are unselective, but the products could easily be separated from
the unknown byproducts of higher polarity, which are likely
oligomers/polymers. With one methyl group as a donor substituent in
the 5-position of the furan, which increases the nucleophilicity of the
furan ring, much higher yields could be obtained.
In 2013 Pyne and coworker developed concise synthesis of α-substituted

2-benzofuranmethamines and 2-subsituted benzofurans via α-substituted

OH Br O OH
R1 R1 R1
R2 R4 Acetone R2 R4
R2 R4
R3 K 2 CO3
R3 R3
1 2 3
Cl
O O
O R1
Cl
Cl R1 t
KO Bu R1 Grubbs cat.
R2
NaOH/H 2O/TBAB R2 R4 R2 R4 R4
R3
R3 R3
4 5 6
a. R 1=R 2=R 3=R 4=H

Cl PCy3 Ph b. R 1=R 2=R 4=H, R 3=CH3
Grubbs cat.= Ru c. R 1 =R2 =R4=H,R3 = OCH 3
Cl
PCy H 3
d. R 1=R 2=R 4=H, R 3=Cl
e. R 1=R 2=R 3=H,R4 = COCH3
f. R 1 =R3 =R4 =H,R2 = COCH 3
Scheme 4.1 New synthesis of benzofurans from phenols via claisen rearrangement and ring-closing metathesis.
RuCl3(10 mol%),AgOTf(30 mol%)

+ +
OH Cu(OTf) 2 (50 mol%), CH3 CN,80ºC O O OH
51% 4% 15%
Scheme 4.2 New synthesis of benzofurans from phenols.
2-benzo-furanmethyl carbocation intermediates (Scheme 4.4) [4]. The

reaction used AgNO3 as the catalyst and reacted in hot DMF.
α-Substituted 2-benzofuran-methamine derivatives could be obtained with
moderate to good yields through sequential cycloisomerization-1,3-allylic
rearrangement.
In 2014 Bi and coworker developed new silver-catalyzed heteroaro-
matization of propargylic alcohols with p-toluenesulfonylmethyl iso-
cyanide, which provides an efficient and modular approach to sulfonyl
benzoheteroles (Scheme 4.5) [5]. In this case, sulfonylation and cycliza-
tion seemed to occur, leading to α-sulfonyl ketones as intermediates.
Upon cyclization and aromatization of the latter, sulfonyl benzofurans
were obtained with good overall yields.
In 2004 Fan and coworker developed silver-catalyzed synthesis of
4-substituted benzofurans via a cascade oxidative coupling-annulation
protocol (Scheme 4.6) [6]. This one-pot cascade reaction involved
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removed. To-day, the 21st, he has been joined by a companion of his
own species, a red-chequered homer; but instead of the mutual
demonstrations of pleasure one would expect to witness at their
meeting in such isolation, they remained quite indifferent to each
other’s presence, the newcomer possibly from motives of disdain, as
he appears to belong to the aristocracy, seeing he sports an
aluminium bracelet, on which are the letters “U.B.” and the year
1901, besides a number composed of three figures, which,
unfortunately, I took no note of. A strong southerly breeze on the
22nd deprived us of their company. Losing the shelter of the tower,
they were unable to make headway against the wind, and,
fortunately for themselves, were driven landwards.
On the 20th a small patch of paidle-fish spawn was seen
cemented in a sheltered nook of the rocks. This is unusually early for
nesting operations, as it is generally May before they are much in
evidence here. The extremely small quantity may denote a change
of mind on the part of the depositor; besides, the site is badly
chosen, as the nest is a couple of feet above low water, and
consequently without the cock’s guardianship for some time each
tide. Possibly the heavy seas prevalent during the past fortnight may
have warned the builder of being somewhat premature in her
operations.
We had ocular demonstration the other day concerning a matter
of which doubts have been expressed, namely, the skinning of their
prey by seals. Not only do they skin their fish, but each shred of skin
is greedily swallowed as soon as stripped. The skinning entails a
good deal of trouble, as the fish is pushed away from the seal at
every mouthful, and consequently sinks, so that a dive is necessary
each time in order to resume operations. Why he should take all this
trouble is not apparent, but presumably he understands his own
business best. His operations at present are watched by us with
longing eyes, for though he appears to have all he wants we are as
yet fishless. However, the presence of the paidle spawn is a hopeful
sign, and is the first attraction for the wandering cod, by whom it is
greedily devoured, providing they can steal a march on the red-
coated sentry—a difficult matter, one would think, considering how
assiduous he is in the protection of his charge. The white whelks,
presumably adopting the promising report of the reconnoitring party
sent out last month, have turned out en masse, and are now waging
a one-sided war of extermination upon the defenceless mussels.
The times change and we change with them. Our present light is
doomed, and what the assaults of almost a century’s gales have
failed to accomplish will succumb to the demands of modern
innovation. Doubtless, the presiding genius of the reef will be
congratulating himself, as he bares his head each tide to witness the
process of demolition, on the return of the palmy days when as yet
no meddling light interfered with the working of his own sweet will in
dealing death and destruction to many a stout ship. Happily, this
view is only apparent, for by early autumn a much more powerful
light will be installed, and a new lease of life granted to the grand old
building which has so effectively served the maritime world since
1811. Probably but few on shore noticed the first appearance of the
temporary light on the evening of the 30th. Of weaker power, but
presenting similar characteristics as the future light, namely, red and
white flashes alternately, with an interval of thirty seconds between
each flash, it will remain in use till ousted by its more powerful
successor.
MAY 1902.
December in May fitly describes the prevailing state of the weather

during this month. Chilling winds, accompanied by snow, hail, or
sleet showers, engender doubts as to the veracity of the calendar,
but the arrival of a number of terns on the 18th dispels all doubts
upon the matter. Sojourning in Africa since their departure in
September, they invariably make their appearance here in May. At
present there are about thirty of these energetic little birds busy
diving among the breakers, picking up small fry, among which is
seen inch long sand eels. A flock of kittiwake gulls also hunt
alongside of them, while several gannets are to be seen further off,
plunging in pursuit of larger game. Clustered in sheltering nooks of
the rock are numerous patches of ova, deposited by the white whelk.
Closely resembling ears of wheat in size and shape, each is
attached to the rock by a short footstalk, terminating in a flattened
disc. On being pressed, a milky fluid, somewhat granular, is exuded
from the free end. The whelks themselves are at present feasting on
limpets, whose shells have been fractured by the debris consequent
on the alterations in progress, though at other times they do not
appear to attack the limpets, their thick shells possibly making the
game not worth the candle.
Despite the inclemency of the weather, the work in connection
with the alterations is being rapidly pushed forward. The removal of
the old lantern and parapet wall turned out a more laborious
undertaking than the erection of the new ones. Strength and stability
were the outstanding features of the old erection, and were carried to
such an extent as would probably be considered superfluous in
these days. The stone parapet wall would in itself be an eye-opener
to our modern jerrybuilders. Octagonal outside, circular within, the
wall was composed of five courses of Craigleith freestone, each
course feathered and grooved, while each stone dovetailed its entire
depth into its neighbour. At each point of the octagon holes were
drilled from top to bottom of the wall to receive the two inch iron bolts
which secured the heavy cast iron lantern to the parapet. It was
necessary to reduce the stones to fragments before hurling them into
the sea, in order to prevent them obstructing the boat tracks or
damaging the gratings. Between the outer and inner linings of the
copper dome a scrap of newspaper was found wrapped round what
appeared to be a file handle. The printed matter was quite legible,
and bore reference to an unfortunate episode, happily long since
relegated to the realms of oblivion, namely, the investigation into the
conduct of the then Princess of Wales in 1806. In one of the
ventilators which pierced the parapet wall on a level with the balcony,
but long since disused, a perfectly desiccated specimen of a wren
was found. Attracted probably by the light while on a migratory
journey, it had evidently taken shelter in the ventilating tube just prior
to its being plugged up with a wad of tow, a material which for many
years has been superseded throughout the service by cotton waste.
The ping-pong craze has come our length, and in imitation of
other manlier sports a trophy has been instituted for competition, the
said trophy to become the property of the holder after being won
thirteen consecutive times. The trophy takes the form of a handsome
cup of silver, or, to be more explicit, of a metal usually found in
conjunction with silver, and is quite Grecian in its simplicity of design.
It is considered to be of foreign origin, and bears evidence of having
at one time been profusely chased and engraved. A beautiful
pastoral scene is depicted on the one side, while, on the other, two
foreign words are barely decipherable, namely, “Lait Concentré.” The
trophy generally graces our tea table for some time prior to the
competition, and materially aids in stimulating the flagging energies
of the competitors.
JUNE 1902.
Only towards the end of this month did we experience anything like
summer weather. Belieing the wintry weather we had been
experiencing, the fragrant odour of the hawthorn blossom borne on
the off-shore wind imparts a pleasurable sensation, recalling scenes
of earlier days when void of care we went “flourish” gathering, or
later on disported ourselves amongst the “hips and haws.” Here, no
sylvan scenery greets the tired eye nor gives respite to the senses
from the everlasting waste of waters, with its ever-changing moods,
from placid glassy calm to the wildest turbulence, when blustering
Boreas drives his team amain, and the white-maned coursers charge
down upon us like an avalanche. As the tide drops, and the long lush
tangles trail their tattered tops on the surface, a dank heavy odour is
perceptible, scarcely so pleasing to the senses as that of the
“hawthorn bud that opes in the month of May.” Equipped with a stout
stick bearing an iron hook, an hour’s crab-hunting among the rocks
brings one into contact with many forms of life otherwise unnoticed.
Groping underneath a projecting ledge, to ascertain if the inmate is
at home, the eye is arrested by minute nodules of scarlet jelly
pendant from the roof, and destined to become a close imitation of
their terrestrial namesake the anemone, or, in similar situations,
patches of white whelk ova appear like so many grains of wheat
arranged as close as possible to each other.
Recently a solitary instance was noticed of a whelk carrying the
ova attached to the exterior of its own shell. Many different species
of whelks are thus met with, some scarcely distinguishable by the
naked eye. The intrusion of the crab-stick soon betrays the presence
of the crab. Gripping the “cleek” in his claws, he prepares for
resistance by forcing his back against the roof of his domicile with all
the power his crooked legs are capable of. Should he feel himself
being drawn he immediately releases his grip, and, if possible,
“seeks his benmost bore.” Should the cleek find a favourable hold,
such as under the armpit, so to speak, he is soon dislodged, but if
the hole be somewhat crooked it is extremely difficult to move him,
and even then he may make his appearance in sections, as he parts
company with the different members of his body on the slightest
provocation, a proceeding about which he has but little compunction,
as he knows well others will soon sprout in their places, a
convenience which Nature might with advantage have extended to
the genus homo. Poachers, it is stated, have made use of these
crustaceans while “ferretting” rabbits, by sending them into the
burrows with a stump of lighted candle stuck on their backs. One can
fancy the surprise with which “bunny” would stand aghast at such a
fearful apparition.
Scarcely a bird is to be seen in our vicinity at present, nesting
operations calling them elsewhere. A few foraging gannets are seen
daily passing and repassing, catering for their sitting mates on the
Bass Rock. The terns and gulls will probably have their wants
supplied from the shores in the neighbourhood of their nurseries.
The nest of the tern is of the simplest description—a slight
depression on a gravelly beach or grassy mound, or even the bare
surface of a rock is considered sufficient for their purpose, nest-
building, in their estimation, being evidently considered superfluous.
It is surprising that the eggs remain in some of the positions in which
they are deposited. I have frequently set them rolling along the rock
surface by the action of my breath. On their exit from the egg the
young are immediately led by the parents to a shingly beach, or
other place of concealment, where it is extremely difficult to detect
them from their surroundings. Here they are fed with sand-eels and
other small fry till such time as they are able to wing their way to the
fishing grounds themselves, though even then they are frequently
the recipients of the parents’ generosity, their hunting powers being
as yet inadequate to supply their needs.
The work in connection with the alterations here progresses
rapidly, and by the end of next month it is expected but little will be
left undone. To all external appearance the work is already finished,
but the building of the huge lens and revolving machinery, along with
the internal fittings, have yet to be completed.
JULY 1902.
Myriads of medusae or jellyfishes are constantly streaming past our

door, apparently without any powers of volition of their own, but
helplessly at the mercy of the tides. Of various sizes, shapes, and
colours, they impart quite a gay appearance to the seascape,
somewhat resembling a grassy sward carpeted with beautiful
flowers—huge sunflowers predominating—the whole moving silently
just beneath the green, glassy surface. Great tremulous discs,
twelve inches in diameter, trail their streaming tentacles several feet
behind them; others, again, no larger than a pea possess the power
of radiating, from the ciliary bands with which they are furnished, all
the colours of the rainbow. Stranded high and dry, what a contrast to
their former glory, now an inert mass of slobbery mucilage. At one
period of their existence they appear quite plant-like in their habits.
Attached to the rocks, they closely resemble miniature fir trees, each
plant ultimately producing whole colonies of juvenile medusae. Fish
have been fairly plentiful this month, but owing to the work at present
in progress we have but little time to avail ourselves of the
opportunity. On the 6th a red chequered pigeon, stamped “J. B.
Sollaway, Beeston,” on wing, was released after a night’s detention.
On Saturday the 12th, other two pigeons were captured at 8.30 p.m.
One a red chequered homer, with aluminium ring on leg marked N.U.
01, H.A. 587, also rubber racing ring on other leg, marked 132
outside and 263 Q inside; the other a blue chequered homer, with
leg ring marked N.U. 99, C. 8953, and racing ring marked Q 513
inside and 174 outside; wing feathers stamped “Walter H. Walker,
Bank House, Horsforth, Leeds.” Both pigeons, after being watered
and fed, were released at 11 a.m. on 13th, each steering a sou’-
westerly course from the Rock.
On the evening of Sunday the 27th our new light was exhibited for
the first time, the coveted honour of “first light” falling in the ordinary
routine of duty to the writer. The new apparatus—a bewildering
arrangement of massive glass prisms—is in striking contrast with its
predecessor, the old reflector system of lighting, a system, by the
way, now almost obsolete. The following description of the new light
is copied from an engraved plate affixed to the new
apparatus:—“Combined hyper-radiant and 1st order apparatus, with
equiangular dioptric elements and catadioptric back prisms; power of
red flash and white flash equalised. White and red flashing light,
showing white and red flashes alternately every half minute, the
period being one minute. Designed by Messrs Stevenson, Civil
Engineers, Edinburgh. Contractors, Messrs Steven & Struthers,
Glasgow, and Messrs Société Des Etablissements Henry Lepaute,
Paris. David A. Stevenson, Engineer to the Board. Apparatus makes
one revolution in one minute—1901.”
Occasionally during the progress of the alterations our population,
unlike that of Arbroath, increased to a somewhat alarming extent,
mounting at times to a grand total of seven all told. Considering that
the majority of the population were unaccustomed to life under such
“cribbed, cabined, and confined” conditions, it was surprising to
witness the cheerfulness and good humour with which they accepted
their sixteen weeks’ solitary confinement. At times the resources of
our commissariat were taxed to their utmost. Beef, which is stored in
our safe on the balcony, and retains its freshness for a fortnight in
cold weather, demands a liberal salting at present, otherwise it does
become a trifle “gamey,” but, on the whole, it is preferable to its
relative in tins—a relationship, by the way, extremely difficult to
prove, and hopelessly so should the label be missing. What though
at times a transverse section of our loaves disclosed a landscape in
cerulean tints undreamt of by the most vivid impressionist, the
transference to “hard tack” was accepted with better grace than
when a similar move had to be made from the salted meat to the
“embalmed commodity.”
AUGUST 1902.
The coating of acorn barnacles with which the higher surfaces of the
Rock and also the base of the tower are whitened in summer is fast
disappearing before the ravages of that ruthless destroyer the white
whelk. Seen from the balcony, this encrustation resembles a lime-
hauled wall, and presents a suitable background for the observation
of moving objects under water. These barnacles are frequently
mistaken by the casual observer for young limpets, whereas, unlike
the limpet, which moves freely from place to place in quest of
vegetable diet, the moment the young barnacle settles to erect his
limey habitation, he possesses a fixity of tenure which terminates
only with his existence. An outer wall, with razor edges, surrounds a
hollow cone, his private apartment, and probably guards his four-
leaved door from injury. This opening, through which all business
with the outer world is transacted, is scarcely discernible when
above water; but immediately the tide covers it, the hollow cone is
seen to fall apart in four vertical sections, a bunch of fingers is thrust
forth and rhythmic clutches made at invisible food. How little they
resemble their relatives who swing by their pendulous stalks from
ships’ bottoms or submerged wreckage, and see the world without
any exertion of their own. The ancients firmly believed that from
these animals certain birds were produced, probably from the
resemblance of their shelly casement to the beak of a bird, and the
bird known as the barnacle-goose owes his name to this belief. Even
to-day there are persons who solemnly declare that the Northern
Diver is so evolved.
Another fallacy common amongst fishing communities on the
West Coast is the attributing the destructive effects of the teredo
navalis, or ship-worm, to the innocent barnacle, whose only fault is
the resistance their multitudes offer to a ship’s progress through the
water. A log of wood which has been adrift at sea for a lengthened
period will generally be found to have its surface clustered with
pendulous barnacles. The removal of these disclose minute pin-
holes on the surface, which, in the interior, assume the diameter of a
man’s little finger, and permeate the log from end to end like a
honeycomb. Each little tunnel is smoothly enamelled with a deposit
of lime by this indefatigable borer, the teredo. Though boring parallel
with his neighbour, the thickness of paper only separating them, they
never, by any chance, encroach on each other’s bore. Their tracks
are seen to abruptly diverge when all but into that of their neighbour,
so that they are evidently cognisant of each other’s proximity, an
interesting fact also apparent in rats on board wooden vessels, who,
though they will gnaw their way through any woodwork, instinctively
refrain from suicidal attempts on the outer skin of the ship.
On the memorable 9th we had a bird’s-eye view of the Coronation
celebrations in Arbroath. With the aid of our telescope the crowds on
the Common were clearly visible, the ladies in white dresses being
most conspicuous. The flash of the guns firing the royal salute was
seen fifty-five seconds before the report reached us. In the afternoon
the sports in the Victoria Park occupied our attention, and the white-
clad competitors in the high jump could be seen taking their
preliminary run and rising over the obstacle. Parties straying on the
beach had only their heads visible, and as they neared the margin
appeared to vanish under water. The progress of the bonfire on the
Common at night was also watched, and the moving figures could be
plainly seen silhouetted in the glare. Probably but few noticed our
attempt to celebrate the occasion. Two strings of flags from the
balcony to the rocks fluttered gaily in the breeze, while the balcony
railing was similarly decked. Amongst those suspended from the rail
was a flag of peculiar interest, namely, one which had been sewn by
Miss Stevenson, a sister of the builder, Robert Stevenson, almost a
hundred years ago. The central subject depicted on the white ground
is the Bell Rock Lighthouse; on the right, the patron saint of Scotland
with his cross; while a ship under full sail occupies the left, the whole
bordered with a deep edging of red. The figures are extremely well
executed, and the colouring to the flesh tints remarkable. The flag
was presented to the Rock by Miss Stevenson to be used as a table
draping during divine service.
Several white butterflies and moths innumerable were seen
passing here this month. It seems these insects have their migratory
periods as well as birds, and at stations favourable for their
observation they appeared, to quote from a writer in a recent number
of “Chambers’s,” “as a dense snowstorm driven by a light breeze,
and this not for one day only, but for many in succession. Whereas
birds come and go with clockwork regularity, the immigration of
butterflies is uncertain, and of all those which survive the perils of the
deep no single one returns.”
SEPTEMBER 1902.
A good deal of heavy weather has been experienced on the Rock

this month, and the stability of our new lantern subjected to a fair
strain, though probably nothing to what it will have to encounter
during the course of the winter. The lantern—composed of gun metal
astragals, narrowed to the utmost limit compatible with strength, in
order to intercept as little light as possible—may be looked upon as a
huge hollow cylinder of glass, which in itself seems but a feeble
barrier to the onslaughts of the storm. But the three tiers of triangular
panes are of heavy plate glass, and the apparently slim like
astragals are braced together in the most effective manner to ensure
the greatest degree of strength, and need cause no uneasiness to
the stranger viewing the outlook during the progress of a gale. It is
awful to think that out in that dark void, amid the warring elements,
fellow beings may be battling for their lives in close proximity to
where we sit in comfort and security, totally ignorant of their
condition, and utterly helpless to render them the slightest
assistance. Probably a case in point occurred during the gale of the
3rd. On the 9th, about noon, we were somewhat surprised to see the
gunboat Seamew approaching the Rock with a hoist of flags,
indicating that they wished to communicate with us. Bringing up
close to the Rock, they signalled, “Have you seen a vessel in
distress?” to which we answered “No”; and then remembering we
had seen a torpedo boat pass the day previous, and fearing another
case of “buckling” had occurred, we asked “Was it a torpedo boat?”
in reply to which they communicated the intelligence, “No; it is a
sailing craft from Anstruther last Wednesday, and seven hands.” On
our replying “We have not seen her,” the signal “Thank you” was
hoisted, and the gunboat steamed out to the eastward on her
sorrowful quest. Passing a torpedo boat at gun practice, she was
seen to signal her also, with the difference that the flags then used
had no existence in our code. Later in the evening she was again
seen making for Dundee.
We have had several takes of fish of late, though there seems to
be a scarcity of “fry” compared with last year, the absence of which
probably accounts for the terns failing to call upon us with their
young for a few weeks’ feasting prior to commencing their migratory
journey southwards. Gannets may be seen at present striking at fish
within a few feet of our doorway, while a flock of young gulls hover
expectantly, with feeble peeping cries anticipating the feast in store
for them when the dinner scraps make their appearance. Further off
a few eider ducks—who only arrived on the 25th, somewhat later
than last year—evidently eye the proceedings of these juvenile
degenerates with disdain, preferring to refrain from such pampered
luxuries and dine on the products of the chase alone. The eiders
present are as yet all adult males, the females presumably still
occupied with family cares teaching the young idea how to shoot, or
rather fish, if plucking mussels, catching crabs, etc., can be called
so, for such is their diet, and does not include fish. Strange that the
foremost arrivals among migratory birds are all males. Why this is so
is not agreed upon by observers, some supposing that the females
are detained by maternal duties; others, again, affirm that they
migrate en masse, and that the more vigorous males soon outstrip
and ungallantly leave the gentler sex to bring up the rear. On the 6th
we had our first intimation of the autumnal migratory flight in the
arrival of a flock of wheatears, accompanied by a solitary wren. On
the 27th several greenfinches, larks, and starlings were making
insane efforts to follow the line of most resistance, resulting in our
new lantern receiving its first baptism of blood, as the glass next
morning testified. Several porpoises are to be seen puffing and
blowing a mile off, and on the 28th a school of “finner” whales were
seen heading north.
I see by the Arbroath Guide that one of our old fog bells has been
presented by our Commissioners to the Arbroath Museum, a fit
resting place after its long sojourn on the Rock. Should the date
upon it happen by any chance to become erased, what possible
controversies it may yet become the subject of amongst posterity as
to its connection with that mythical personage “Ralph the Rover.” I
myself can testify to its having conformed in one respect at least with
that of the poem, for on lowering it from its position on the balcony
for shipment the tide had overflowed the Rock about a couple of feet,
causing the bell to settle with an audible gurgle, or as one of the
seamen (Fraser) appropriately quoted, “The bell sank down with a
gurgling sound.”
OCTOBER 1902.
We have had occasional visits of feathered migrants during the

month, but it is a matter of remark that each year sees a decrease in
the number of arrivals here. Probably the increased number of lights
on our coast accounts for this diminution, some proving more
attractive than ours. A few years ago it was quite on the cards at this
season of the year—thanks to the migratory instinct—to have an
additional course at dinner, to which fieldfares, blackbirds, and
redwings were the voluntary contributors, and even at times the
gamey woodcock “graced the groaning board”—for our “board,”
being double-leaved and somewhat senile, does occasionally groan,
and this without reference to any superincumbent strain. Amongst
the more noteworthy of our captures here, at various times, the
following may be mentioned:—A peregrine falcon, large horned owl,
small brown owl, kestrels, sparrow hawks, crows, cormorants, corn-
crakes, and a turtle dove. Birds generally arrive here in a fagged
condition, and are easily captured. As an instance, a kestrel landed
on our balcony railing during fog, and, despite the explosions of our
fog-signal twenty feet overhead, tucked his head under his wing and
fell sound asleep. Another arrival of note was a common blue
pigeon, which, after a few hours’ stay, surprised us by depositing an
egg in our doorway. Disturbed on our appearance, it reluctantly
deserted its treasure, but not without many backward glances before
spreading its wings shorewards.
Podley-fishing has been fairly successful during the month, and
several codlings have been taken from the pools at low water. Whilst
photographing lately, another of our number was busy endeavouring
to extract a breakfast from Port Hamilton. Hooking a fair sized
codling, the camera was turned on the scene, and fish à la photo
figured in our bill of fare next morning. A few years ago a photo was
taken of a paidle cock and hen, both of which were taken from their
nests for this purpose, and proved amenable sitters; the cock
appearing in the photo quite conscious of his importance, though the
hen appeared somewhat bored, having been snapped in the middle
of a huge “gape,” which some of my previous sitters might interpret
as a yawn. Both were returned to their nests none the worse of their
unique experience, and possibly yet relate their feelings before the
camera to the admiring wonder of fishy audiences, till puffed with the
idea of their own importance they now probably suffer from a
disease (peculiar to some higher vertebrates with as slender a
reputation) resulting in what is colloquially known as “swelled head.”
Wouldn’t the fishermen of Arbroath fancy their lines had fallen in
pleasant places should the fish they pursue at such hazard come
sailing voluntarily into the harbour, and even without the usual
ceremony of dropping them a line, appear on the surface, mutely
asking to be lifted out? Such, however, was our experience lately.
Shortly before daybreak one quiet morning our attention was
attracted by the movements of a few gulls, evidently interested in
some object in the water at the edge of the reef. As daylight
advanced it was seen to be a large fish wobbling erratically upon the
surface. On extinguishing the light and descending to the rocks,
which the advancing tide had not yet covered, the fish was seen to
have entered the Johnny Gray boat track, and was propelling itself,
keel upwards, in our direction. A fish in this unusual position
indicates an abnormal distension of the swimming bladder, which, by
over-increasing its buoyancy, entirely upsets its centre of gravity, and
forces it topsy-turvy to the surface. A steam trawler, which had been
working close to the Rock for several days previous, was probably
responsible for our friend’s “blown” condition. Stepping gingerly over
beds of white whelks as we wade bare foot to welcome our visitor,
we mentally contrast our inferiority with more juvenile days—a time
when even road metal could be safely negotiated. The screaming
gulls resent our interference with their expected feast, no doubt
slanging us unmercifully as we land our capture, an arm-long lythe,
safely on the grating. Their clamouring, however, is soon stilled, as
each retires with as big a share of the offal as his strength and agility
can command.
The long-tailed ducks are now only wanting to complete the list of
our winter boarders, and their advent may be looked for early next
month. The eiders have now attained their numerical strength for the
winter, and are busily engaged picking up a living, not only for
themselves, but also for the parasitical gulls which hover in close
attendance, shepherding them with unwearied diligence. The
peculiar cackling of the eiders—not unlike that of wild geese—
becomes somewhat disturbing as their operations are occasionally
carried on underneath our bedroom window. Gannets are now rarely
seen here, but at their breeding haunts on the Bass Rock—which we
had the opportunity of visiting while on our way here last relief—they
are still in evidence, though by the end of the month they will have
commenced their journey southwards. A new light is being
completed on the Bass Rock, and on the first of December, yet
another factor in our dwindling list of visitors will be in operation—
ostensibly a lighthouse—but to our feathered friends, alas! a
veritable slaughter-house.
NOVEMBER 1902.
Exceedingly stormy weather, with a prevalence of sou’-easterly

winds and heavy seas, has been our portion here this month,
restricting our movements out of doors, till with circling round our
promenade on the balcony one almost doubts the possibility of ever
again being able to hold a straight course when opportunity offers.
Workmen have been engaged this month fitting up a service of
copper piping from the grating at the base of the tower to the cisterns
in the oil store on the third flat, whereby the operation of storing oil
will in future be rendered much easier. The oil will now be landed in
forty-gallon casks, instead of the small six-gallon ankers as formerly,
emptied into a sifting tank on the grating, and by means of a rotary
pump forced upwards to the oil cisterns—a vast improvement on the
old system, when each anker had to be hoisted indoors, and then
shouldered upstairs to the cisterns.
A pleasing incident of the month was the arrival of a handsome
present for each of the keepers, consisting of a silver mounted briar
pipe, a pound of golden bar tobacco, and a liberal supply of first
class reading matter. All keepers throughout the service—over 200—
were similarly supplied, so that the gift will be seen to be a pretty
extensive one, and the donor, James Coats, junr., Paisley, has
without doubt earned the gratitude of the service by this generous
act of kindness.
About the beginning of the month we had a few feathered visitors,
chiefly blackbirds, fieldfares, and starlings. On the morning of the 5th
several struck heavily on the lantern, but were swept away by the
strong sou’-east wind then blowing. The gannets have now all
disappeared, none having been seen since the 27th. The eiders
continue in close attendance and have had their numbers
augmented by the arrival of the longtails on the 9th, a week earlier
than last year, thus completing our list of regular boarders for the
winter. At 6 p.m. on the 13th we were privileged with the unusual
spectacle of a lunar rainbow. The bow—a faint white arc against the
dark background—was distinctly visible in the nor’-west, though, of
course, void of the vivid colouring inseparable from its solar
namesake.
While taking a turn round the balcony on the evening of the 15th,
our attention was attracted to what appeared to be a peculiar shaped
mass of foam resting on the rocks immediately beneath us. On
careful observation, however, the object was seen to move slightly in
the faint moonlight, and by the aid of our telescope the outline of a
seal could be dimly seen. On the change of the watch at 6 p.m. an
attacking party, including the workmen then on the Rock, was
organised, and a plan of campaign drawn up. Descending the
outside ladder, which was fortunately in deep shadow, we were able
to gain a footing on the Rock unperceived. His suspicions had,
however, evidently been aroused, as he was seen to lift his head
sniffing uneasily in our direction. Bracing ourselves within the margin
of the shadow cast by the tower, we charged down upon him at the
double, expecting to see him beat a hasty retreat to the water; but, to
our surprise, he made no effort whatever in that direction, but
seemed to consider himself quite a match for us, and that there was
no present necessity for retreating. Snarling and snapping viciously
as we surrounded him, he appeared at a great disadvantage
compared with his agile movements when in his element, his hind
flippers being now of practically little use to him, his lumbering
movements being effected by the aid of the fore flippers alone. His
furious efforts to sample portions of our anatomy were easily
avoided, and by laying hold of his hind flippers, as one would trundle
a barrow, he was immediately placed hors-de-combat. An
unfortunate squid or cuttlefish, which had been left stranded by the
receding tide, when pushed within his reach was seized and
energetically shaken with all the vim of an accomplished ratter. The
wooden shaft of a boat-hook was similarly treated, and still bears
evidence of his utter ignorance of the dental profession. A rope being
procured, a clove hitch was slipped over one of his hind-flippers, the
other end made fast to an eye-bolt on the Rock. Thus secured, he
was left to his novel reflections for the night.

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Transition Metal-Catalyzed Benzofuran

Synthesis 1st Edition Xiao-Feng Wu

The Chemical Transformations of C1 Compounds 1st

Transition-Metal-Catalyzed C-H Functionalization of

Metal-Catalyzed Asymmetric Hydrogenation. Evolution and

Transition Metal Oxides for Electrochemical Energy

Renewable Polymers and Polymer-Metal Oxide Composites:

Metal Oxide Nanostructures Chemistry: Synthesis from

Metal-free synthetic organic dyes Kruger

Atomically Precise Metal Nanoclusters Thalappil Pradeep

Xiao-Feng Wu and Yahui Li

For Information on all Elsevier publications

Publisher: John Fedor

In this volume, the progress of transition metal-catalyzed furan

MeO OMe OMe

Scheme 1.1 Selected examples of benzofuran derivatives.

Transition Metal-Catalyzed Benzofuran Synthesis. DOI: http://dx.doi.org/10.1016/B978-0-12-809377-1.00001-2

In 1986, Marinelli and coworkers developed a palladium-catalyzed

Later, Kundu and coworkers reported palladium-catalyzed hetero-

Scheme 2.1 Palladium-catalyzed synthesis of benzo[b]furan from alkynes.

Scheme 2.2 Palladium-catalyzed synthesis of benzo[b]furan from alkynes.

Transition Metal-Catalyzed Benzofuran Synthesis. DOI: http://dx.doi.org/10.1016/B978-0-12-809377-1.00002-4

Scheme 2.3 Palladium 2 thiourea catalyzed carbonylative annulation of o-hydroxylarylacetylenes.

Yang and coworkers developed an effective cocatalysis system

In 2003, the same group reported synthesis of conformationally

Scheme 2.4 Synthesis of 2,3-diarylbenzo[b]furan by the Pd-catalyzed.

The key step of the previous three approaches is attack of a nucleo-

Substrate Product Yield

Scheme 2.5 Palladium-catalyzed intramolecular o-arylation of enolates.

In 2004, Pan and coworkers reported the synthesis of

PdCl2 (5 mol%), (n-Bu) 3N

(1-n-butyl-3-methylimidazolium tetraborate) and substituted-benzo[b]

Scheme 2.7 Synthesis of benzo[4,5]furopyridines via palladium-mediated reactions.

R''' 8 mol% 1,5-cyclooctadiene

(CH 2) 4Cl (CH 2) 5CH 3

92% 91% 94%

Scheme 2.8 Synthesis of 2,3-disubstituted benzofurans by platinum-olefin-catalyzed arboalkoxylation of alkynyl-

Scheme 2.9 Possible mechanism.

Scheme 2.10 Palladium-catalyzed annulations of 2-alkynylphenols to form 2-substituted 3-halobenzo[b]furans.

Substrate 1 Disulfide 2 Yield

(or diselenides) for the synthesis of 3-chalcogen-benzo[b]furans. The

In 2008, Aurrecoechea and coworkers developed a new

Entry Alkene Product Yield

Scheme 2.12 Palladium-catalyzed cyclization of 2-alkynylphenols and alkenes.

More recently, Sridhar Reddy and coworkers palladium-catalyzed

In 2015, Chen and coworkers reported one-pot synthesis of

In 2015, Valdes and coworkers reported Pd-catalyzed synthesis of

Entry Product Yield

Scheme 2.13 Synthesis of α-benzofuranylacetamides via oxypalladation and isocyanide insertion.

Entry Product Yield

Scheme 2.14 One-pot synthesis of benzofurans.

Scheme 2.15 Possible mechanism.

H 4-Me 2N-C 6 H4 50%

Scheme 2.16 Palladium-catalyzed synthesis of benzofurans.

R'' Pd(TFA) 2 (5 mol%), CuI (1 equiv.) S Ar

Entry Product Yield

Scheme 2.17 Palladium-catalyzed synthesis of 3-sulfenylbenzofurans.

Scheme 2.18 Palladium-catalyzed synthesis of benzofurans and proposed mechanism.

In 2016, Liu and coworkers reported palladium-catalyzed C H

In 2016, Zhou and coworkers reported the synthesis of (Z)-α-tri-

Scheme 2.19 Synthesis of 3-trifluoromethylbenzofuran.

In 2011, Li and coworkers reported palladium-catalyzed selective

In 1998, Bumagin and coworkers developed Pd21-catalyzed