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Transition Metal-Catalyzed
Pyridine Synthesis
Pyridine Synthesis
Heterocycle Synthesis Series
Xiao-Feng Wu
Department of Chemistry, Zhejiang Sci-Tech Univeristy, China
and
Leibniz-Institut für Katalyse e.V., Universität Rostock, Germany
AMSTERDAM • BOSTON • HEIDELBERG • LONDON

NEW YORK • OXFORD • PARIS • SAN DIEGO
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Elsevier
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ISBN: 978-0-12-809379-5
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DEDICATION
Dedicated to my wife, children, and my parents

Thanks for their understanding, support, encouragement,
and tolerance!
CHAPTER
Introduction
1
Pyridine is an important class of nitrogen-containing heterocycles found
in various natural products, pharmaceuticals, and materials (Scheme 1.1).
Based on its importance, numerous synthetic procedures have been devel-
oped for their preparation [1]. In this book volume, the main achieve-
ments on transition metal-catalyzed pyridines synthesis are discussed.
Based on the reaction types, the whole volume is catalogued by intramo-
lecular cyclization and intermolecular cyclization reactions.
NH2 Cl Cl HO
S
P OEt OH
Cl N O OEt HO
Chlorpyrifos N
SO2
N N Vitamin B6
H Cl
Sulfapyridine O
N
N
H
Cl
F3C N NH
Anticancer
NH2
Cl
NC CO2Et
N
Antifungal O N
N Herbicide
Cl N NH
N Insecticide
NO2
O N
H
Cl N S
N O O
N
Rabeprazole
N
H Clarinex
Scheme 1.1 Selected examples of bio-active pyridine derivatives.
Transition Metal-Catalyzed Pyridine Synthesis. DOI: http://dx.doi.org/10.1016/B978-0-12-809379-5.00001-9

© 2016 Elsevier Inc. All rights reserved.
2 Transition Metal-Catalyzed Pyridine Synthesis
O N O
N
N
O S O
S
NH NH
O
Rosiglitazone O Pioglitazone
O N O N
H H
N S N S
O CF3 O
N N O
Lansoprazole F
O Pantoprazole
SO2Me
F
Cl N
Etoricoxib H
N N
N N N
N
H HN
N .HOMs
H N O
N Anabasine Imatinib Mesylate
Scheme 1.1 (Continued)
REFERENCE
[1] Reviews on pyridines synthesis see:
a. Gromov, S. P.; Fomina, M. V. Russ. Chem. Rev. 2008, 77, 1055 1077.
b. Chopade, P. R.; Louie, J. Adv. Synth. Catal. 2006, 348, 2307 2327.
c. Bönnemann, H. Angew. Chem. Int. Ed. Engl. 1985, 24, 248 262.
d. Heller, B.; Hapke, M. Chem. Soc. Rev. 2007, 36, 1085 1094.
e. Baumann, M.; Baxendale, I. R. Beilstein J. Org. Chem. 2013, 9, 2265 2319.
f. Weding, N.; Hapke, M. Chem. Soc. Rev. 2011, 40, 4525 4538.
g. Domínguez, G.; Pérez-Castells, J. Chem. Soc. Rev. 2011, 40, 3430 3444.
h. Neely, J. M.; Rovis, T. Org. Chem. Front. 2014, 1, 1010 1015.
i. Hill, M. D. Chem. Eur. J. 2010, 16, 12052 12062.
j. Varela, J. A.; Saá, C. Chem. Rev. 2003, 103, 3787 3801.
k. Bull, J. A.; Mousseau, J. J.; Pelletier, G.; Charette, A. B. Chem. Rev. 2012, 112,
2642 2713.
l. Gulevich, A. V.; Dudnik, A. S.; Chernyak, N.; Gevorgyan, V. Chem. Rev. 2013, 113,
3084 3213.
m. Allais, C.; Grassot, J.-M.; Rodriguez, J.; Constantieux, T. Chem. Rev. 2014, 114,
10829 10868.
n. Amatore, M.; Aubert, C. Eur. J. Org. Chem. 2015, 265 286.
o. Henry, G. D. Tetrahedron 2004, 60, 6043 6061.
p. Kotha, S.; Brahmachary, E.; Lahiri, K. Eur. J. Org. Chem. 2005, 4741 4767.
q. Pla-Quintana, A.; Roglans, A. Molecules 2010, 15, 9230 9251.
r. Varela, J.; Saá, C. Synlett 2008, 2571 2578.
CHAPTER 2
Synthesized by Intramolecular Cyclizations
Intramolecular cyclization of substrates to the corresponding pyridine

derivatives is the most straightforward pathway. By intramolecular
version reaction, the positions of substituents are fixed and easier to
control, such as N-propargylic β-enaminones in pyridines and pyrroles
synthesis. In 2008, Cacchi et al. reported a copper-catalyzed synthesis
of polysubstituted pyridines from N-propargylic β-enaminones [1]. By
using DMSO as the solvent, pyrroles can be produced in good to high
yields in the presence of only Cs2CO3 at room temperature, while pyri-
dines can be formed under the assistant of CuBr at 60 80 C (Scheme
2.1). Here, the N-propargylic β-enaminones can be prepared via the
following sequences: (1) cross-coupling of terminal alkynes with acyl
chlorides; (2) followed by the conjugate addition of propargylamine
with the resultant α,β-enones; (3) further Sonogashira cross-coupling
of the propargyl derivative with aryl halides.
Scheme 2.1
A Carousel Tube Reactor (Radley Discovery), equipped with a magnetic
stirrer, was charged with substrate (0.23 mmol) and recrystallized CuBr
(13 mg, 0.09 mmol) in anhydrous DMSO (3 mL) was stirred for 1.5 h
under argon at 60 C. Ethyl acetate was added to the reaction mixture
and the resulting mixture was washed first with a 0.1 N HCl solution,
then with a saturated NaCl solution, and finally dried over Na2SO4. The
solvent was removed under vacuum and the residue was purified by chro-
matography (SiO2, 30 g, n-Hexane/AcOEt 70/30 v/v) to give the corre-
sponding pyridine derivative.

O R′ O R″
CuBr (0.4 equiv.) 10 examples
R N R 51–76%
H DMSO (6 mL), 60–80°C
R″ R′ N
O R″
R' N
O
O R′
Cs2CO3 (2 equiv.) R R″
16 examples
R N
H DMSO (3 mL), rt 42–96%
R″ R′ N
H
Scheme 2.1 CuBr-catalyzed pyridines synthesis from N-propargylic β-enaminones.
A procedure by using enamino ester and alkynone as the substrates

was developed as well [2]. 2,3,4,6-Tetrasubstituted pyridines were pre-
pared in a single step. Various acids, such as acetic acid, Amberlyst 15
ion exchange resin, zinc(II) bromide or ytterbium(III) triflate, can be
applied as promoter for the cyclization step of the Michael addition
adduct. 4-(3-Oxoalkyl)isoxazoles found could be applied as starting
material for pyridine synthesis as well [3].
In 2013, Kim and coworkers reported a palladium-catalyzed dom-
ino cyclization of N-(2-bromoallyl)-N-cinnamyltosylamides for the
construction of pyridines [4]. The reaction proceeds via a domino 5-
exo/3-exo carbopalladation, ring expansion by palladium rearrange-
ment, and an aromatization. Various 4-arylnicotinate derivatives were
produced in good yields (Scheme 2.2).
Scheme 2.2
A mixture of substrate (0.5 mmol), Pd(OAc)2 (6 mg, 5 mol%), PPh3
(13 mg, 10 mol%), and Cs2CO3 (408 mg, 2.5 equiv.) in DMF (1.5 mL)
was heated to 120 C for 3 h. The reaction mixture was poured into dilute
HCl solution and extracted with diethyl ether. The organic solvent was
removed by evaporation, and the residue was purified by flash column
chromatography (hexanes/ether, 3:1) to afford the pure product.
Synthesized by Intramolecular Cyclizations 5
CO2R Ar
Pd(OAc) 2 (5 mol%), DMF
Ar RO 2C 12 examples
PPh3 (10 mol%), 120°C 41–75%
N
Ts Br Cs2CO3 (2.5 equiv.), 3 h N
Ts
N
Ts N
PdBr Ar
Ar CO2R
O PdBr
RO
Ts N Ts
N
Ar
Ar CO2R
O BrPd
RO
Scheme 2.2 Pd-catalyzed pyridines synthesis from N-(2-bromoallyl)-N-cinnamyltosylamides.
In 2014, Gagosz and coworkers reported their achievement on gold-

catalyzed transformation of 2H-azirines to the corresponding functio-
nalized pyridines [5]. Good yields of polysubstituted functionalized
pyridines were produced from easily accessible 2-propargyl 2H-azirine
derivatives (Scheme 2.3). High functional-group tolerance and wide
substrate scope were exhibited. Later on, a DFT study was performed
[6]. They show that the reaction was promoted by the gold(I) catalyst
through 1,5-endo-dig cyclization by nucleophilic attack, direct ring
expansion (C-N bond cleavage) followed by 1,2-proton transfer.
Scheme 2.3
To a solution of 0.10 0.20 mmol (1.0 equiv.) of the azirine in 1,2-dichloro-
ethane (0.1 M) was added tBuXPhosAuNTf2 (2 mol%). The solution was
heated to reflux until TLC analysis indicated completion of the reaction (ca.
1 12 h). The solvent was removed under reduced pressure and the crude
product was purified by column chromatography. The silica gel used for col-
umn chromatography was deactivated with diethylamine prior to use.
R′ R′
R′″O2C tBuXPhosAuNTf 2 (2 mol%) R′″O2C
R″
N
DCE, 85°C R N R″
R
23 examples
62–99%
Scheme 2.3 Au-catalyzed pyridines synthesis from azirines.

Eastgate and coworkers developed a Ni-catalyzed C-H functionali-

zation procedure for the synthesis of pyridine core and applied in the
synthesis of the potent JAK2 inhibitor BMS-911543 [7]. With nickel
oxide supported on silica (PRICAT) as the catalyst, 74% of the key
intermediate can be achieved (Scheme 2.4).
Scheme 2.4
To a pressure vessel charged with hydroxyamidine (50.0 g, 0.164 mol, 1.0
equiv.) in AcOH (0.650 L, 13.0 mL/g) and PhMe (0.500 L, 10.0 mL/g)
was added Piv2O (30.5 g, 0.164 mol, 1.0 equiv.) followed by PhMe
(0.150 L, 3.0 mL/g). The pressure vessel was degassed with N2, and the
reaction mixture was stirred at 20 30 C for 0.5 h. PRICAT (9.00 g,
18 20 wt%) as a slurry in AcOH (0.100 L, 2.0 mL/g) and PhMe (0.1 L,
2.0 mL/g) was added and the pressure vessel degassed with nitrogen and
then pressurized with hydrogen (3 psig). The reaction mixture was stirred
at 20 30 C for 20 h. Upon completion, the hydrogen was purged from
the pressure vessel with nitrogen. The reaction mixture was filtered
through a plug of Celite, and the cake was washed with PhMe
(2 3 0.150 L, 2 3 3.0 mL/g). The reaction mixture was concentrated, dis-
solved 3 3 in PhMe (0.250 L, 5.0 mL/g), and concentrated to remove
excess AcOH. To the residue was added PhMe (0.200 L, 4.0 mL/g), and
the mixture was warmed to 50 C for 2 5 h to effect crystallization. The
mixture was cooled to 0 C and stirred for an additional 2 5 h. The solids
were filtered, washed with PhMe (2 3 0.100 L, 2 3 2.0 mL/g), and dried
in vacuo to provide the AcOH salt of aminopyridine.
N N
EtO N N
PRICAT (20 wt%), AcOH EtO
O N N NH2 Piv 2O (1 equiv.), toluene O N N NH2

OH
74%
N
N N
N N
O N N N
H
BMS-911543
Scheme 2.4 Ni-catalyzed synthesis of JAK2 inhibitor BMS-911543.

Reddy’s group reported a silver-catalyzed annulation of enynyl

azides to pyridine derivatives in 2015 [8]. 3,6-Disubstituted pyridines
were prepared in good yields through Ag-mediated aza-annulation of
2-en-4-ynyl azides which were derived from MBH-acetates of acetyle-
nic aldehydes. 5-Iodo-3,6-Disubstituted pyridines can be prepared
from enynyl azides having an electron-rich substituent on the alkyne
functionality with I2 as the promoter (Scheme 2.5).
Scheme 2.5
To a stirred solution of alkynyl azide (1 equiv.) in 1,2-dichloroethane
(3.0 mL) was added AgSbF6 (0.3 equiv.) and TFA (2 equiv.) at 80 C.
After completion of the reaction, the mixture was quenched by saturated
NaHCO3 and stirred for 30 min. The mixture was extracted with
CH2Cl2, organic layer was washed with H2O, brine, dried over Na2SO4,
and concentrated in vacuo. The residue was purified by column chroma-
tography on silica gel (EtOAc: hexanes) to afford the corresponding
product.
To a solution of azide (1 equiv.) in CH2Cl2 and NaHCO3 (1 equiv.)
was added at 0 C followed by the addition of iodine (5 equiv.), the solu-
tion was stirred at room temperature for given time. After completion of
the reaction, the mixture was quenched with Na2S2O3 solution and
extracted with EtOAc, organic layer was washed with H2O, brine, dried
over Na2SO4, and concentrated in vacuo. The residue was purified by col-
umn chromatography on silica gel (EtOAc: hexanes) to afford the corre-
sponding product.
O O
AgSbF 6 (30 mol%) 14 examples
R′ R′
60–86%
R TFA, DCE, 80°C
N3 R N
O O
I
R′ I 2 (5 equiv.), DCM R′
8 examples
21–92%
R NaHCO3, rt
N3 R N
Scheme 2.5 Ag-mediated synthesis of pyridines from enynyl azides.
A Lewis acid mediated reaction of acyclic vinyl allenes and imines

to produce tetrahydropyridines was developed by Palenzuela and cow-
orkers in 2012 [9]. The cycloadducts can be transformed into polysub-
stituted pyridines, including bipyridines, by catalytic transfer
hydrogenation using cyclohexene as hydrogen donor in good yield

(Scheme 2.6). The reaction was extended to the aromatization of the
bicyclic cycloadducts prepared in previous works from the reaction of
semicyclic vinyl allenes and imines, yielding tetrahydropyridines.
Metathesis was applied in heterocycle synthesis as well and can be fur-
ther transformed into the corresponding pyridines [10].
R′ R′
Pd/C (10 mol%; 50 wt%), reflux 5 examples
45–71%
MeOH, Cyclohexene
R N R″ R N R''
Ph
R R′
R R′
R″ Pd/C (10 mol%; 50 wt%), reflux
R″
N R″′ MeOH, Cyclohexene
N R″′
Ph 7 examples
41–83%
Scheme 2.6 Pd/C-catalyzed synthesis of pyridines from tetrahydropyridines.
Movassaghi and Hill developed a ruthenium-catalyzed cycloisomeri-

zation of 3-azadienynes to the corresponding pyridines [11]. The alkynyl
imines were produced from a variety of N-vinyl and N-aryl amides by
amide activation and nucleophilic addition of copper(I) (trimethylsilyl)
acetylide sequence reaction. Then by Ru-catalyzed protodesilylation and
cycloisomerization, the desired pyridine derivatives were formed selec-
tively in good to excellent yields (Scheme 2.7). For the reaction mecha-
nism, C-silyl metal vinylidene was found to be the key intermediate.
Scheme 2.7
An oven dried pressure vessel containing a magnetic stir bar was charged
with ammonium hexafluorophosphate (587 mg, 3.60 mmol, 1.00 equiv.),
CpRuCl(PPh3)2 (262 mg, 0.35 mmol, 0.10 equiv.), and SPhos (148 mg,
0.35 mmol, 0.10 equiv.) under a nitrogen atmosphere in a glove-box and
the flask sealed and brought out of the glove-box. Imine (3.60 mmol,
1 equiv.) and toluene (18 mL) were subsequently added via syringe. The
flask was flushed with argon, sealed, stirred, and placed in an oil bath at
105 C. After 19 h, the reaction vessel was allowed to cool to ambient
temperature and the mixture was transferred to a recovery flask with a
20-mL portion of dichloromethane. This solution was concentrated under

reduced pressure and the residue was purified by flash column chroma-
tography on silica gel (15-50% EtOAc/Hexanes) to afford the quinoline
as pure product.
Ar′
N CpRuCl(PPh 3) 2 (10 mol%), toluene Ar′
N
Ar SPhos (10 mol%), NH4PF6 (1 equiv.), 105°C
TMS Ar
Ar′ Ar′
N N
RuLn
Ar Ar RuLn
Ph S
N NTIPS
N N
Ph N
Ph Ph
Ph
77% 73% 64% 99%
S O
N 97% N 70%
Ph Ph
Scheme 2.7 Ru-catalyzed synthesis of pyridines from 3-azadienynes.
Hanzawa, Saito, and their coworkers developed a rhodium(I)-cata-

lyzed intramolecular hetero-[4 1 2] cycloaddition of σ-alkynyl-vinyl
oximes in 2007 [12]. By using [RhCl(cod)]2 and AgSbF6 as the catalyst
system in hexafluoroisopropanol (HFIP), bicyclic pyridine derivatives
were formed in good yields (Scheme 2.8).
R′ R′
OMe [RhCl(cod)] 2 (5 mol%), rt–80°C
Y N Y N
X AgSbF 6 (13 mol%), HFIP X
R R
Y = CO, X = O 10 examples
Y = CH2, X = O, NTs, C(CO 2Et) 2 15–86%
Scheme 2.8 Rh-catalyzed synthesis of pyridines from σ-alkynyl-vinyl oximes.

Zhang and Gao studied the silver(I)-catalyzed cyclization reaction

of ortho-alkynylaryl aldehyde oxime derivatives [13]. A dramatic sub-
stituent effect was found in this transformation. When the oxime
substituted with an alkyl group, this Ag(I)-catalyzed reaction gave iso-
quinolines good to excellent yields in dimethylacetamide at 110 C, in
contrast, isoquinolin-1(2H)-ones were produced in moderate to high
yields in dimethylformamide at room temperature when the oxime
substituted with an acetyl group. In the case of substrates without an
aromatic ring, Ph3PAuOTf gave better yields than AgOTf (Scheme
2.9). Later on, Reddy and coworkers developed an AuCl3-catalyzed
intramolecular cyclization of aromatic o-alkynyloximes and 2-
alkynylcycloalkene-1-carbaldoximes for the formation of isoquinoline
and pyridine derivatives [14].
Ph
[Catal] (5 mol%) Ph AgOTf: 37%
N Ph3PAuCl/AgOTf: 63%
N DMAc, 110°C
OMe
Ph
Ph [Catal] (5 mol%) Ph Ph
AgOTf: 58%
N DMAc, 110°C N Ph 3PAuCl/AgOTf: 77%
OMe
Scheme 2.9 Ag/Au-catalyzed synthesis of pyridines from oximes.
Park and coworkers developed a highly efficient procedure for the

synthesis of 3-hydroxypyridines in 2012 [15]. With dirhodium complex
Rh2(tfacam)4 (tfacam 5 trifluoroacetamide) as the catalyst and δ-diazo
oxime ethers as substrates, based on carbenoid-mediated NaO bond
insertion, a variety of pyridines were produced in 5 10 min in good to
excellent yields. Recently, they reported their new achievements on
transformation of α-diazo oxime ethers to pyridines with rhodium as
the catalyst (Scheme 2.10).
Scheme 2.10
To a stirred suspension of Rh2(tfacam)4 (2 mol%) in dichloroethane was
added a solution of diazo compound in dichloroethane under nitrogen,
and the reaction mixture was stirred under reflux until the diazo com-
pound was completely consumed (detected by TLC). The solvent was
evaporated under reduced pressure to give crude compound which was
purified by flash column chromatography using hexane : ethyl acetate

(9:1) to give desired products.
A solution of diazo compound (0.2 mmol) and Rh2(OAc)4 (0.004 mmol,
2 mol%) in chlorobenzene (2.0 mL) was stirred at 130 C until the starting
material was fully consumed. The reaction mixture was concentrated under
reduced pressure to give the crude material which was purified by flash
chromatography using hexane: ethyl acetate (9:1) to give desired products.
OMe R″
N R′ N2 Rh 2(tfacam) 4 (2 mol%) OH 15 examples
N
R R″ DCE, reflux 60–92%
O R R′
OMe MeO R″
N R′ [Rh] O
N
R R″
O R R′
OMe
N O R′ Rh 2(OAc)4 (2 mol%) N
R′,R″ 12 examples
R R″ PhCl, reflux 64–80%
R
N2 CO2Me
OMe H
N O R′ NiCl2(PPh3)2 (10 mol%) N
R 18 examples
R′,R″ 44–92%
R R″ PhCl, 130°C
N2 MeO2C
Scheme 2.10 Rh-catalyzed synthesis of pyridines from diazo compounds.
More recently, a visible-light-promoted cyclization of acyl oximes to

pyridine derivatives via iminyl-radical was published by Yu, Zhang, and
coworkers (Scheme 2.11) [16]. With fac-[Ir(ppy)3] as the photoredox cat-
alyst, the acyl oximes were converted by 1e2 reduction into iminyl radi-
cal intermediates, which then underwent intramolecular homolytic
aromatic substitution (HAS) to give the N-containing arenes. The reac-
tions proceeded in high yield at room temperature with a broad range
of substrates. This strategy of visible-light-induced iminyl-radical forma-
tion was successfully applied to a five-step concise synthesis of benzo[c]-
phenanthridine alkaloids.
Scheme 2.11
A 10 mL round bottom flask was equipped with a rubber septum and
magnetic stir bar and was charged with substrate (0.2 mmol, 1.0 equiv.),
fac-Ir(ppy)3 (0.002 mmol, 0.01 equiv.). The flask was evacuated and back-
filled with N2 three times. DMF (4.0 mL, 0.05 M) was then added with
syringe under N2. The mixture was then irradiated by a 5W white LEDs
strip. After the reaction was complete (as judged by TLC analysis), the
mixture was concentrated under vacuum to remove DMF. The residue
was then purified by flash chromatography on silica gel (EtOAc:
hexane 5 1:10) to afford the pure product.
O2CC6H4p-CF 3
N fac-[Ir(ppy) 3] (1 mol%) R″ COR
Ar R′ DMF, 26°C, visible light
R″ COR Ar N R′
14 examples
45–91%
Scheme 2.11 Light-promoted synthesis of pyridines from acyl oximes.
Additionally, the intramolecular cyclization of diyne-cyanohydrin

(two alkynes and one cyano) has been explored as well based on the
concept of (2 1 2 1 2) cyclization [17]. In 2007, Cheng and coworkers
reported a cobalt-catalyzed intramolecular [2 1 2 1 2] cocyclotrimeriza-
tion of nitrilediynes for the construction of tetra- and pentacyclic pyri-
dine derivatives (Scheme 2.12) [18]. By using CoI2(dppe)/Zn as the
catalytic system at 80 C in CH3CN, various highly substituted nitrile-
diynes were transformed into the corresponding products in good to
excellent yields (Scheme 2.12). Afterwards, several modified cobalt
catalyst-based systems were also developed [19 21].
Scheme 2.12
A 25 mL round-bottomed side-arm flask containing CoI2(dppe)
(0.005 mmol), Zn (2.75 mmol) was evacuated and purged with nitrogen
gas three times. To the flask were then added nitrilediyne (1.00 mmol)
and CH3CN (3.0 mL) via syringes. The reaction mixture was allowed to
stir at 80 C for 12 h. At the end of the reaction, the reaction mixture was
diluted with CH2Cl2, filtered through Celite and silica gel, and the filtrate
was concentrated. The crude residue was purified through a silica gel col-
umn using hexanes and ethyl acetate as eluent to give pure products.
NC
CoI2(dppe) (5 mol%), 80°C
Zn (2.75 equiv.), CH3CN (3.0 mL) N

S
S
16 examples
46–94%
NC
Co N
Co
S
S
Scheme 2.12 Cobalt-catalyzed synthesis of pyridines from nitrilediynes.
Rhodium catalysts were applied in this type of transformation as

well. Notably, by the addition of enantioenriched C2-symmetric spiro-
bipyridine ligands, the reaction proceeded in an enantioselective man-
ner (Scheme 2.13a) [22]. More recently, cyano-yne-allenes were found
to be suitable substrates as well [23]. 2,6-Naphthyridine derivatives can
be produced selectively here (Scheme 2.13b).
O R
R N
[Rh(cod) 2]BF4 (5–10 mol%), DCM, rt O
NC X X
X (R)-Segphos or (R)-H 8-BINAP (5–10 mol%)
NC X
O (a)
R N
R 8 examples
O
70–99% yields
18–71% ee
X Z
Z N
[RhCl(PPh 3)3] (10 mol%), 120°C
X N 8 examples (b)
NEt 3 (5 mol%), PhCl, MW 38–66%
Y
Y
X, Y = NTs, O, C(CO2Et)2
Z = CH2, CH2CH2, etc.
Scheme 2.13 Rh-catalyzed synthesis of pyridines from nitrilediynes.

REFERENCES
[1] Cacchi, S.; Fabrizi, G.; Filisti, E. Org. Lett. 2008, 10, 2629 2632.
[2] Bagley, M. C.; Brace, C.; Dale, J. W.; Ohnesorge, M.; Phillips, N. G.; Xiong, X., et al.
J. Chem. Soc., Perkin Trans. 2002, 1, 1663 1671.
[3] Ohashi, M.; Kamachi, H.; Kakisawa, H.; Stork, G. J. Am. Chem. Soc. 1967, 89, 5460 5461.
[4] Kim, K. H.; Kim, S. H.; Lee, H. J.; Kim, J. N. Adv. Synth. Catal. 2013, 355, 1977 1983.
[5] Prechter, A.; Henrion, G.; dit Bel, P. F.; Gagosz, F. Angew. Chem. Int. Ed. 2014, 53,
4959 4963.
[6] Jin, L.; Wu, Y.; Zhao, X. J. Org. Chem. 2015, 80, 3547 3555.
[7] Fitzgerald, M. A.; Soltani, O.; Wei, C.; Skliar, D.; Zheng, B.; Li, J., et al. J. Org. Chem.
2015, 80, 6001 6011.
[8] Reddy, C. R.; Panda, S. A.; Reddy, M. D. Org. Lett. 2015, 17, 896 899.
[9] Regás, D.; Afonso, M. M.; Palenzuela, J. A. Tetrahedron 2012, 68, 9345 9349.
[10] a. Donohoe, T. J.; Bower, J. F.; Basutto, J. A.; Fishlock, L. P.; Procopiou, P. A.; Callens,
C. K. A. Tetrahedron 2009, 65, 8969 8980.
b. Donohoe, T. J.; Bower, J. F.; Baker, D. B.; Basutto, J. A.; Chan, L. K. M.; Gallagher,
P. Chem. Commun. 2011, 47, 10611 10613.
c. Donohoe, T. J.; Basutto, J. A.; Bower, J. F.; Rathi, A. Org. Lett. 2011, 13, 1036 1039.
d. Yoshida, K.; Kawagoe, F.; Hayashi, K.; Horiuchi, S.; Imamoto, T.; Yanagisawa, A.
Org. Lett. 2009, 11, 515 518.
[11] a. Movassaghi, M.; Hill, M. D. J. Am. Chem. Soc. 2006, 128, 4592 4593.
b. Hill, M. D.; Movassaghi, M. Synthesis 2007, 1115 1119.
[12] Saito, A.; Hironaga, M.; Oda, S.; Hanzawa, Y. Tetrahedron Lett. 2007, 48, 6852 6855.
[13] Gao, H.; Zhang, J. Adv. Synth. Catal. 2009, 351, 85 88.
[14] Subbarao, K. P. V.; Reddy, G. R.; Muralikrishna, A.; Reddy, K. V. J. Heterocycl. Chem.
2014, 51, 1045 1050.
[15] a. Qi, X.; Dai, L.; Park, C.-M. Chem. Commun. 2012, 48, 11244 11246.
b. Jiang, Y.; Park, C.-M. Chem. Sci. 2014, 5, 2347 2351.
[16] Jiang, H.; An, X.; Tong, K.; Zheng, T.; Zhang, Y.; Yu, S. Angew. Chem. Int. Ed. 2015, 54,
4055 4059.
[17] Lan, Y.; Danheiser, R. L.; Houk, K. N. J. Org. Chem. 2012, 77, 1533 1538.
[18] Chang, H.-T.; Jeganmohan, M.; Cheng, C.-H. Org. Lett. 2007, 9, 505 508.
[19] Meißner, A.; Groth, U. Synlett 2010, 1051 1054.
[20] Miclo, Y.; Garcia, P.; Evanno, Y.; George, P.; Sevrin, M.; Malacria, M., et al. Synlett 2010,
2314 2318.
[21] Zhou, Y.; Porco, J. A., Jr.; Snyder, J. K. Org. Lett. 2007, 9, 393 396.
[22] Wada, A.; Noguchi, K.; Hirano, M.; Tanaka, K. Org. Lett. 2007, 9, 1295 1298.
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2882 2885.
b. Garcia, L.; Pla-Quintana, A.; Roglans, A.; Parella, T. Eur. J. Org. Chem. 2010, 3407 3415.
CHAPTER 3
Synthesized by Intermolecular Cyclizations
3.1 SYNTHESIZED BY [2 1 2 1 2] CYCLIZATION REACTIONS

Formal [2 1 2 1 2] cyclization reactions are the most explored transi-
tion metal-catalyzed procedures for pyridines synthesis. In this section,
the main achievements on this topic will be discussed based on the cata-
lyst systems applied. Takahashi’s group reported a methodology for the
synthesis of pyridines, pyridones, and iminopyridines from two different
alkynes and a nitrile via azazirconacycles [1]. In the presence of 1 equiv.
of NiCl2(PPh3)2, through azazirconacyclopentadienes intermediate only
single products of pyridine derivatives from two different symmetrical
alkynes and a nitrile can be achieved. In the same period, Sato and their
coworkers developed a titanium(II) alkoxide-mediated pyridine synthe-
sis from two different unsymmetrical acetylenes and a nitrile [2].
Notably, tris(acetonitrile) complex [Fe(C5Me5)(CH3CN)3][PF6]-medi-
ated [3] and cobalt-mediated [4] versions were reported as well. In 1977,
Vollhardt and Naiman reported their work on CpCo(CO)2 catalyzed
synthesis of pyridines [5]. By refluxing in o-xylene, 47% of the desired
pyridine can be produced from 1,7-octadiyne and cyanoacetic ester.
Heller and coworkers performed cobalt-catalyzed photochemical syn-

thesis of pyridines [6]. Ethyne, propyne, butyne, dimethylbutyne, benzo-,
aceto-, trimethoxybenzonitrile, n-butylcyanoacetate, tert-butylcyanide
and etc. were all tested as substrates. And cobalt complexes YCo(cod)
were applied as the catalysts (Y 5 η5-cyclopentadienyl, η5-indenyl, η5-tet-
raphenylcyclopentadienyl, η5-acetylcyclopentadienyl, η3- cyclooctenyl, η6-
1-phenylborinato, and so on). Very high chemoselectivities were obtained
at low alkyne concentrations. The regioselectivity can be advantageously
influenced by the properties of the ligands in the precatalyst and by the
application of bulky nitriles and alkynes. Both artificial light and
sunlight can also be employed as the radiation sources without loss of
selectivity. Remarkably, by using chiral cobalt(I) complexes as the
catalysts, the reaction can be realized in an asymmetric manner.
Hagiwara, Hoshi, and coworkers applied this concept in the synthesis
of chiral 2,20 -bis(pyridin-2-yl)-1,10 -binaphthyl ligands from enantio
pure 2,20 -dicyano-1,10 -binaphthyl with 1,6-heptadiyne, 1,7-octadiyne,

1,8-nonadiyne, and 2,8-decadiyne [7]. Microwave heating was applied
in [2 1 2 1 2] cocyclization as well [8]. Kotora and coworkers reported
a methodology for the preparation of a series of (pyridin-2-yl)purine
derivatives in 2008. Good yields of pyridines were produced from
6-(diynyl)purines and nitriles in the presence of a stoichiometric or cata-
lytic amount of [CpCo(CO)2] enhanced by microwave. Alkyl, aryl, and
heteroaryl cyanides are all suitable substrates for this transformation.
Deiters and coworkers developed a solid-supported version of
[2 1 2 1 2] cocyclization of alkynes and nitriles for pyridines synthesis
[9]. By using CpCo(CO)2 (20 mol%) as the precatalyst and tetramethy-
lammonium oxide (TMAO) as the catalyst activator at 80 C, good
yields of the desired pyridines can be achieved. In the procedure, one
of the alkyne was immobilized on the resin and cleaved under mild
conditions using 1% TFA in DCM. More recently, Hapke and Thiel
supported air-stable CpCo(I)-complex [CpCo(trans-MeO2CCH
CHCO2Me){P(OEt)3}] [10] in order to enhance its recyclability [11].
By covalently linking this highly active catalyst on silica-bound ana-
logue support, pyridine derivatives can be produced in good yields by
cyclotrimerization of a diyne and a nitrile.
A systematic study on the use of [CpCo(CO)(dmfu)] (dmfu 5 dimethyl
fumarate) [12] as a precatalyst for the cocyclization of alkynes and
nitriles was published in 2011 [13]. By this catalyst, the incorporation
of electron-deficient nitriles into the pyridine core was realized. 3- or
4-Aminopyridines can be produced regioselectively by modifying the
substitution pattern at the yne-ynamide. Based on DFT computations,
the author suggested that 3-aminopyridines are formed by formal [4 1 2]
cycloaddition between the nitrile and the intermediate cobaltacyclopenta-
diene, whereas 4-aminopyridines arise from an insertion pathway.
This catalytic system was applied in the synthesis of bicyclic 3- or
4-aminopyridines from yne-ynamides and nitriles (Scheme 3.1) [14].
Scheme 3.1
To a solution of the starting ynamide in toluene were added the nitrile
and CpCo(CO)dmfu under inert atmosphere. After being refluxed for
15 h and allowed to cool to rt, the mixture was purified by flash chroma-
tography eluting first with petroleum ether and then (unless otherwise
noted) with petroleum ether/ethyl acetate (9:1).
Synthesized by Intermolecular Cyclizations 17
R′
n CpCo(CO)(dmfu) (10 mol%) n 15 examples
R′CN N N 36–100%
N toluene, 110°C, 15 h
Ts Ts n = 1, 2, 3
R R
Scheme 3.1 Co-catalyzed synthesis of 3- or 4-aminopyridines.
Saá and coworkers reported a one-step procedure for the synthesis of

spiropyridines in 1999 [15]. The desired pyridines can be obtained in
moderate yields by Co(I)-catalyzed double cocyclization between bis-
alkynenitriles and alkynes (Scheme 3.2). The products can be applied as
C2-symmetric chiral ligands and a diastereomeric mixture of tetracoor-
dinated [CuIL2] complex with 7,70 -spiropyridine was prepared as well.
R
R n
CpCo(CO)2 (30 mol%) R N
N R
n n toluene, reflux
NC CN
R R n
10 examples
R = H, TMS, Ph, CO2Me 7–33%
n = 1, 2
Scheme 3.2 Co-catalyzed synthesis of spiropyridines.
In 2008, Schreiber’s group studied the cycloaddition of silyl-

tethered diynes with nitriles [16]. The tether provided high regioselec-
tivity, and no exogenous irradiation required while using THF as the
solvent with catalytic amount of CpCo(CO)2. Moderate to excellent
yields of the desired products can be achieved (Scheme 3.3). One of the
resulting bicyclic and monocyclic (desilylated) pyridines was identified
as an inhibitor of neuregulin-induced neurite outgrowth
(EC50 5 0.30 μM) in a screen that probes a pathway likely to be
involved in breast cancers and schizophrenia.
Scheme 3.3
Diisopropyl(pent-1-yn-3-yloxy)-(phenylethynyl)silane (10.0 mg, 0.033 mmol)
was placed into an oven dried sealed tube and dissolved in degassed THF
(0.67 mL). Nitriles (0.05 mmol, 1.5 equiv.) were added to the stirring
solution. After complete dissolution, a solution of cyclopentadienylcobalt
(I) dicarbonyl (1.8 mg, 0.010 mmol, 30 mol%) in degassed xylenes (50 μL)
was introduced by syringe, giving a pale yellow solution that was
submerged into an oil bath preheated to 140 C. After 24 h, the dark brown
solution was cooled to ambient temperature and loaded onto a 4 g silica
plug. Filtration was performed using an Isco Combiflash system using a
gradient solvent commencing with hexanes and ending with 1/1 hexanes/
ethyl acetate (total volume of approximately 40 mL), which effectively
removed insoluble cobalt byproducts. Pooled fractions were concentrated
in vacuo and assayed for conversion by 1H NMR. Purification was
performed by silica gel chromatography using an Isco Combiflash 12 g
column with 20:1 hexanes/EtOAc as eluant, providing the corresponding
pyridines.
R1 R2
Si R R1 R2
O 12 examples
CpCo(CO) 2 (25–30 mol%) Si
R N O 30–98%
R3 R'CN
n THF, 140°C n = 0, 1
R' n R3
R4
R4
OMe Ph OMe Ph
iPr
MeO
MeO
N Si iPr TBAF, THF N
O 23°C, 18 h OH
MeO MeO
inhibitor of the neuregulin/ErbB 4-dependent signaling pathway
Scheme 3.3 Co-catalyzed synthesis of silylated pyridines.
In the same year, Deiters and coworkers developed an approach for

the construction of anthracenes and 2-azaanthracenes via [2 1 2 1 2]
cyclotrimerization [17]. Good yields of the products can be isolated
and tests in fluorescence emission and the fluorescent labeling of mam-
malian cells were performed as well (Scheme 3.4). These compounds
have unique photochemical and biological properties and can act as
environmentally sensitive dyes, metal sensors, pH sensors, and cellular
stains.
Scheme 3.4
The diyne (20 mg, 0.13 mmol), nitrile (1.3 mmol), dry toluene (4 mL),
and CpCo(CO)2 (1.56 μL, 0.013 mmol) were added to a flame dried
microwave vial equipped with a stir bar. The vial was flushed with nitro-
gen, capped with a microwave vial septum and irradiated for 20 min in a
CEM Discover microwave synthesizer at 300 W. After cooling, the reac-

tion was purified by silica gel chromatography, eluting with hexanes/
EtOAc. Due to compound instability, the products were only character-
ized via NMR and directly subjected to the next reaction without HRMS
measurement.
The precursors, DDQ (1.2 equiv.), and dry toluene (2 mL) were added
to a flame dried microwave vial equipped with a stir bar. The vial was
flushed with nitrogen, capped with a microwave vial septum and irradi-
ated for 5 min in a CEM Discover microwave synthesizer at 300 W.
The azaanthracenes (0.02 mmol) and MeI (13 μL, 0.2 mmol) were
added to a flame-dried vial under nitrogen atmosphere. The reaction mix-
ture was heated at 60 C overnight. After cooling to room temperature,
the solvent was removed under reduced pressure to yield the desired pro-
ducts in quantitative yield.
CpCo(CO)2 (10 mol%) R

6 examples
RCN 80–94%
toluene, 120°C, MW N
DDQ (1.2 equiv.)

toluene, 120°C, MW
R R
MeI (10 equiv.) 6 examples
N 60°C, argon N 53–85%
6 examples
99%
Scheme 3.4 Co-catalyzed synthesis of azaanthracenes.
A highly practical method for the catalytic formation of substituted

pyridines from a variety of unactivated nitriles and α,σ-diynes was
developed by Okamoto and coworkers in 2007 [18]. With 5 mol% of
dppe/CoCl2-6H2O as the catalyst in the presence of Zn powder (10 mol
%), pyridines were produced in good yields with high functional com-
patibility and regioselectivity at rt to 50 C (Scheme 3.5). This system
was also applied in the synthesis of polymers by polymerization of
diyne-nitrile monomers [19]. With 2-(2-(hept-2-yn-1-yl)non-4-yn-1-yl)
malononitrile or 2,2-di(but-2-yn-1-yl)malononitrile as the substrate, the
corresponding polymers can be selectively produced.
Scheme 3.5
To a mixture of diyne (1.0 mmol), nitrile (1.5B20 mmol) and zinc powder
(6.5 mg, 0.10 mmol) in NMP (0.6 mL) was added a solution of CoCl2-
6H2O (11.9 mg, 0.05 mmol) and dppe (23.9 mg, 0.06 mmol) in NMP
(0.4 mL) (see note below). The resulting mixture was stirred at ambient
temperature. After completion of the reaction checked by TLC analysis,
Et2O (5 mL) was added and the mixture was filtered through a pad of
Celite with ether (5 mL). The filtrate was concentrated in vacuo and chro-
matographed on silica gel to give the corresponding substituted pyridine.
R′
R′
R
CoCl2.6H2O (5 mol%), NMP
X RCN X
DPPE (5 mol%), Zn (10 mol%), rt–50°C N
R″
22 examples
R″ 39–97%
Bu
MeO2C Me MeO2C Ph
MeO 2C Me
MeO2C N N
MeO2C N
MeO 2C
84% Bu
97% 87%
Bu O
Me TMS Me
MeO 2C
O Me
N MeO2C N 77%
N
Bu O
Et O
83% Me
88% N
O 52%
N
N
O
MeO 2C Me
O
, DMS
T BA F N 86%
TMS 50°C MeO 2C
THF,
MeO 2C Me Ph
N
MeO 2C
Br Br
Ph CCl 2
4, reflu MeO 2C Me
x
97%
N
MeO 2C
Ph
Scheme 3.5 CoCl2-catalyzed synthesis of pyridines.

Schmalz and Nicolaus applied Co-catalyzed cyclization in the syn-

thesis of pyridine incorporated allocolchicine analogues [20]. Started
from readily accessible 3,4,5-trimethoxybenzaldehyde or 3,4,5-tri-
methoxyacetophenone, the (racemic) target compounds were regiose-
lectively obtained in 1520% overall yield (five steps; Scheme 3.6).
R
R
MeO MeO O
O CpCo(CO) 2 (20 mol%)
R' MW, 150°C, PhCl, R″CN MeO
MeO R′
OMe OMe
N
R″
4 steps 10 examples
15–20%
O
MeO
R
MeO
OMe
Scheme 3.6 Co-catalyzed synthesis of allocolchicine analogues.
Saá, Vollhardt, and their coworkers applied cobalt catalyst in the

synthesis of Lysergene and LSD [21]. Lysergene is a naturally occurring
clavine. LSD is also known as lysergide (INN), is a psychedelic drug of
the ergoline family, well known for its psychological effects and mainly
used as an entheogen and recreational drug. By using 4-ethynyl-3-
indoleacetonitriles and alkynes as the substrates in the presence of
cobalt catalyst, the core structures can be prepared (Scheme 3.7).
Complanadine A is a member of the large family of lycopodium alka-

loids, it’s naturally from the club moss Lycopodium complanatum. It
has been reported to induce the secretion of neurotrophic factors from
1321N1 cells, promoting the differentiation of PC-12 cells. Maturely,
complanadine A is likely synthesized through the union of two molecules
of lycodine. In 2010, Siegel and coworkers applied Co(I)-mediated
[2 1 2 1 2] in the total synthesis of Complanadine A (Scheme 3.8) [22].
Saá, Castedo, and coworker applied cobalt(I)-catalyzed [2 1 2 1 2]

cycloaddition in the synthesis of bipyridines and terpyridines in 1997
[23]. By using 5-hexynenitril, 6-heptynenitrile 2-ethynylpyridines, and
2,6-bis[(trimethylsilyl)ethynyl]pyridines as the substrates, the desired
CN R′
R′
CpCo(CO) 2 (1.12 equiv.)
N R
hv, 65–70°C, THF
R″ N
N R″
5 examples
R
6–36%
O
N
N N
H
N N
LSD H H Lysergene
Scheme 3.7 Co-mediated synthesis of Lysergene and LSD cores.
H H
H N
Bn
N CpCo(CO)2 (0.4 equiv.)
Bn
CN 140°C, 1,4-dioxane
N
N N
CHO
TMS
CHO
N N
TMS H
H
N N HN
H
Complanadine A H
N
Scheme 3.8 Co-mediated synthesis of Complanadine A.
pyridine derivatives can be produced in moderate to good yields

(Scheme 3.9a). Later on in 1998, they developed a new, one-step
method for the synthesis of annelated symmetric 3,30 -substituted 2,20 -
bipyridines from acyclic precursors [24]. By using CpCo(CO)2 as the
catalyst, with 5-hexynenitrile and 1,3-diynes as the starting materials,
bipyridines can be selectively produced (Scheme 3.9b).
Scheme 3.9b
A solution of diyne (0.72 mmol), 5-hexynenitrile (0.2 g, 2.17 mmol), and
[CpCo(CO)2] (0.22 mmol) in toluene (10 mL) was irradiated for 1 h under
Ar in a round-bottomed flask equipped with a reflux condenser. The
reaction vessel was irradiated with a Philips PF 808 300 W tungsten slide
projector lamp placed ca. 5 cm from the center of the flask and operated
at 225 W. The volatile components were removed under vacuum and the
residue was chromatographed on silica gel (100:0 to 90:10 EtOAc/
MeOH).
R'
n
R' N
N
R CpCo(CO) 2 (15–30 mol%)
n
N hv, toluene, reflux (a)
N
n = 1, 2
N
n
N R'
R
N
N
R
R
CpCo(CO)2 (30 mol%)
7 examples
hv, toluene, reflux 9–77%
N
R
(b)
R
N
R N
Scheme 3.9 Co-catalyzed synthesis of bipyridines.
Okamoto and coworkers reported a cobalt-catalyzed cycloaddition

reaction of nitriles and α,σ-diyne to the synthesis of substituted
2,20 -bipyridines and 2,20 :60 ,2v-terpyridines in 2008 [25]. A variety of
substituted 2,20 -bipyridines were synthesized by a 1,2-bis(diphenylpho-
sphino)-ethane (DPPE)/cobalt chloride hexahydrate (CoCl2 6H2O)/
zinc-catalyzed [2 1 2 1 2] cycloaddition reaction from the
corresponding substrates with excellent regioselectivity (Scheme 3.10).
More specifically, symmetrical and unsymmetrical 1,6-diynes and
2-cyanopyridine reacted in the presence of 5 mol% of dppe, 5 mol% of
CoCl2 6H2O and 10 mol% of zinc powder to provide the correspond-

ing 2,20 -bipyridines. Under identical reaction conditions, 1-(2-pyridyl)-
1,6-diynes and nitriles reacted smoothly to produce 2,20 -bipyridines in
good yield. 2,20 -Bipyridines were also obtained by the double
[2 1 2 1 2] cycloaddition reaction of 1,6,8,13-tetraynes with nitriles.
Similarly, 2,20 :60 ,2v-terpyridines were synthesized from 1-(2-pyridyl)-
1,6-diyne and 2-cyanopyridine.
Scheme 3.10
To a stirred mixture of zinc powder (3.5 mg, 0.05 mmol), diyne or tetra-
yne (0.5 mmol) and nitrile (1.580 equiv.) in NMP (1 mL) was added a
solution of CoCl2 6H2O (6 mg, 0.025 mmol) and DPPE (12 mg,
0.03 mmol) in NMP (1 mL) at room temperature. The mixture was then
stirred at room temperature or at 50 C. The reaction progress was moni-
tored by TLC analysis. After completion of the reaction, a small portion
of EtOAc or ether was added and the mixture was passed through a pad
of Celite with EtOAc or ether. The filtrate was concentrated to dryness
and the residue was chromatographed on silica gel using hexane/AcOEt
to give the corresponding bipyridine derivative.
N R
R CoCl2.6H2O (5 mol%), NMP
X N
X
R′ N DPPE (5 mol%), Zn (10 mol%), 50°C N
8 examples R′
47–91%
R
R′
X
R N N
X CoCl2.6H2O (5 mol%), NMP
DPPE (5 mol%), Zn (10 mol%), 50°C N
R′
N
6 examples
54–89%
R
R′
R X
N
X CoCl2.6H2O (5 mol%), NMP N
X R′ DPPE (5 mol%), Zn (10 mol%), 50°C

N
R X
5 examples
R′
X = O, CH(CO 2Et)2 41–90%
R
Scheme 3.10 CoCl2-catalyzed synthesis of bipyridines.

One direction for the development in this area is looking for more
active and stable complex. In 2011, Hapke and coworkers prepared
CpCo(H2C 5 CHSiMe3)2 complex and was found active in [2 1 2 1 2]
cycloaddition reactions [26]. The other direction is the exploration of
applications. In 2005, Maryanoff and coworkers applied [2 1 2 1 2]
cycloaddition reaction in the preparation of macrocycles [27]. In the
presence of CpCo(CO)2, pyridine containing macrocycles were pre-
pared from long-chain α,σ-diyne and nitriles, cyanamides, or isocya-
nates (Scheme 3.11). The regioselectivity of these reactions was
affected by the length and type of linker unit between the alkyne
groups, as well as by certain stereoelectronic factors.
N R
R pTol R pTol
CpCo(CO)2 (15 mol%)
o-xylene, 140°C N N
O
O
O n O O
O O O
n O
n = 2, 3
O
EtO 2C
EtO 2C 7
Scheme 3.11 Co-catalyzed synthesis of pyridine containing macrocycles.
In addition to cobalt catalysts, ruthenium catalysts were applied in

[2 1 2 1 2] cycloaddition reactions as well. In 2001, Itoh and coworkers
reported a ruthenium-catalyzed cyclization of 1,6-diynes with dicya-
nides to produce the desired bicyclic pyridines in good yields [28]. By
applying Cp Ru(cod)Cl (Cp 5 pentamethylcyclopentadienyl) as the
catalyst, good yields of the products can be achieved (Scheme 3.12).
Meanwhile, they explored the catalyst system in cyclization of 1,6-
diynes with electron deficient nitriles as well. The desired bicyclic pyri-
dines can be isolated in moderate to high yields [29]. Later on, in 2005,
Yamamoto and coworkers performed systematic studies on this
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Iberian women in ancient days.
In the battlefield it is often dread of the women’s scorn which
drives the men to make the utmost efforts to return victorious.
“This trait reminds one of the Iberian maidens, who chose their
husbands from amongst the bravest warriors.”
Descent on the mother’s side alone ennobles, and the children
belong to the family of the wife.
For instance, the son of a nobly born woman and a slave is
acknowledged as free born, whereas the son of a slave and a free
man remains a slave. But, in favour of the latter, certain tribes have
created a particular caste called “Iradjenat,” who, though yet slaves,
are exempt from certain heavy labour.
It must be added that the women have entire control over their
own property.
Inheritance in the tribes goes from a man to his brother, and, in
default, to the son of a sister, but never to the direct progeny.
In such communities misconduct on the part of women is not
tolerated, it is simply punished with death. Captain Bissuel relates
that a native of the province of Setif killed his sister by order of his
father, they having learnt that she was leading a dissolute life. Both
father and brother mourned for the poor culprit, but were convinced
that they had only done their duty.
On the other hand, according to Duveyrier, the Tuareg lawfully
claim le droit du seigneur from their female slaves, before these
marry.
The same custom is mentioned by Herodotus as obtaining
amongst the Adyrmachidæ in the neighbourhood of Egypt.
The western Tuareg regard this custom as despicable.
The Tuareg have to give their wives a dowry, which varies in
amount. The western Tuareg, for instance, give at least six camels, a
negress, and a complete costume.
These are the principal features of Tuareg customs. They have
many points in common with those of the mystical Amazons and the
Iberians of antiquity.
Even now among the Basques the man plays a subordinate part.
The woman rules and controls the house. “The husband is her head
servant,” who brings to the house only himself and his labour,
together with a stipulation for progeny.
The Arabs.
The Arabs in Tunisia are, like those in Algeria, nearly all nomads.
They reside chiefly in the southern and central portions of the
Regency.
They are recognisable by their tall, slender figures, their lean,
muscular build, and by their dignified nobility of carriage.
The Arab cast of countenance is narrow, the nose curved, the lips
thin and graced by a delicate black beard, the black eyes are lively,
but the expression crafty.
The Arab woman is endowed with a pretty, well-formed figure, but
she is of small stature. She is, on the whole, attractive, but fades
early, being old and ugly through hard work by the time she attains
her twentieth year. Unlike the Berber woman, she is usually obliged
to go abroad veiled.
As the Bey was too weak to collect his own taxes, he united the
various groups of nomad Arabs to form his auxiliary troops. These
tribes were thence designated “Mahzen,” were almost exempt from
taxation, or only paid in kind, such as oil, dates, etc. In return they
bound themselves to fight the robber bands (Jish) who frequently
harassed the country. Were they victorious, all spoils were theirs.
Their ostensible duty was to assist the Bey’s own soldiers to recover
the taxes. This collection resolved itself into sheer plunder. The least
of their perquisites was the right to “diffa” and “alfa,” which means
hospitality for themselves and their horses; of this they took
advantage to the greatest extent, often pillaging wherever they
appeared.
For instance, the holy city of Kairwan was often compelled to raise
forced contributions under this pretext.
Their morals, as a rule, are very lax. The abduction of married
women and girls is common, and adultery a matter of course.
The upbringing that an Arab woman receives in a tent is not
exactly calculated to ensure in any way a moral tone. A young girl is
from the very outset of her innocent life apt to see and learn much
that to us appears offensive.
Whereas the man has every possible right of control over his wife,
she has only the “justice of God” (el hak Allah), meaning that he
must fulfil his obligations towards her as her husband, failing which
she can demand a divorce, not an infrequent occurrence.
After the enactment of the law emancipating slaves, the men in
some tribes married their negresses, with a view to thus evading the
law. But it befell that the former went into court and complained that
they were defrauded of their rights as wives.
Although the Arabs, as aliens, have always been in a minority in
the land of the Berbers, yet they were the masters until the arrival of
the French. They had steadily spread themselves over all the open
plains and lower tablelands, moving ever from east to west. Thus
each tribe continually changed its territory, one tribe ever pressing
another before it farther westward.
Long before Mohammed’s day this immigration had already
begun, but it was not until after his time that it made any real
headway, and the conquest of the country and its conversion to
Mohammedanism took place.
Not until much later, in the middle of the eleventh century, was the
great migration accomplished, in which both Mongols and Egyptians
were included. Such great waves, however, always cause a counter
wave. When the tribes reached the shores of the Atlantic on the
most distant coasts of Morocco, the tide turned. Thus the tribe that
claims to be the chief of all the tribes, namely, the Shorfa, or
“Followers of the Prophet,” is precisely that which, having been to
Morocco, returned eastwards.
Yet another receding wave brought back the “Arabs” who had
conquered Spain, and who were afterwards driven forth again.
These Spanish “Arabs” were for the most part Berbers who had
been carried westward by the tide, and who returned, after a long
sojourn on the Iberian peninsula, blended with other races—
Ligurians, Iberians, Celts, and Western Goths.
The greater proportion of these refugees, who are known in
Barbary as “Andaluz,” established themselves in the towns, where
they introduced a new strain into the already mixed race of Moors.
These Spanish Moors are more especially represented in Tunis.
It is quite natural that, in a country so often invaded and peopled
by foreigners who to this day have never really amalgamated, there
should be an entire lack of patriotism such as is found in Europe. It is
as Mussulmans that these races have united to make war against
the Christian. Amongst themselves they are often at enmity.
Mohammedanism.
Though it is an undoubted fact that the various races of Berbers
and Arabs have preserved much of their identity, it is also noticeable
that, to a stranger arriving in the country for the first time, the
inhabitants appear, as it were, to be fused into one race. This fusion
is the result of their creed, for Mohammedanism has been drawn like
a veil over the whole country.
Mohammed, through the Koran, gave to even daily labour the
stamp of religion, and in a marvellous way moulded all the various
races, who thus became “the faithful,” into one mode of thought and
life, which gradually shaped them all to one pattern, although
hereditary inclinations and customs contended, and are still
contending, against such constraint.
The features which appear most strongly marked in these various
races who have become Mussulmans, are their individual absorption
in their religion and their family organisation.
The stubborn influence of Islamism on the community is entirely
expressed in the phrase “Mektub” (it is written). Fatalism has
destroyed all initiative, all progress. How men may act is immaterial.
“It is written.”
To the Mussulmans, authority is of divine origin. Their creed
ordains that everyone must bow to authority. This has given rise to
the most complete absolutism, alike from the Bey, whose title is “The
chosen of God and the owner of the kingdom of Tunisia,” down to
the lowest of officials.
But yet the yoke may prove too heavy—then the oppressed revolt,
as has so often happened.
The influence of religion is manifest in the treatment of the insane,
whose utterances are held as sacred. The number of real and
pretended lunatics is consequently very great. Hospitality is not
exactly gladly offered to such afflicted persons, but they are
permitted to take whatever they please from a house, a liberty often
very widely interpreted. Latterly a madman in Tunis declared several
houses to be under a ban. All the inmates at once fled, and could not
be persuaded to return. This individual was also inspired with the
sublime idea of erecting a barricade in one of the most populous
streets, by means of doors which he lifted from their hinges.
The Prophet organised the family on the lines best adapted to the
nomad tribes, who were destined to be great conquerors. He
ordained the absorption of the vanquished into the family; while the
males were killed or, if fortunate, made slaves, the women were
allowed to enter the family.
This was the foundation of the rapid conquest of North Africa by
Islam.
To ensure unity in the family, composed of so many and varied
elements, the man is invested with the most absolute authority. He
does not marry but he buys his wife, who becomes his property. He
is unquestionably her lord and master, he can maltreat her, kill her if
she is untrue to him, without risking injury to a hair of his own head.
All that he owes her is the “hak Allah.”
Crimes against women are more rare now through fear of the
French; but as there is no legal census, many murders may be
committed which are never brought to light.
Religious influence first and foremost, also life in common under
equal conditions of many generations of different extraction, have
obliterated many of the characteristics of the natives of Tunisia.
Many Berber tribes have been entirely transformed into Arabs, and,
on the other hand, many Arab tribes have been Berberised. Indeed,
there are tribes forming a subdivision, of which it is well known some
are Berbers, some Arabs.
Of the religious brotherhoods, so numerous elsewhere under
Islam, there are comparatively few in Tunisia. We find the
“Tidyanya,” “Medaniya,” and the “Aissaua,” and, besides these,
many scattered “Shorfa.”
In the towns there is more fanaticism than in the country. In this
respect “those who can read and write are the worst.”
Yet many customs and reminiscences may be found of a former
age before Mohammedanism was forced on the Tunisians.
For instance, the people hang bits of rag all over sacred trees;
many fear the “evil eye,” or honour five as a peculiarly lucky number.
For this reason they set the mark of their own five fingers on their
houses to protect the latter. Indeed, it is not uncommon for a man
who has more than five children, if questioned as to their number, to
reply that he has five, rather than be obliged to name an unlucky
number.
If rain is long delayed, they take refuge in exorcism, and will on
occasion even dip their kaid in a fountain so that his beard may be
wetted—that surely brings rain.
The Moors.
Nowhere has all origin of race been so entirely effaced as in the
towns. There have sprung up the Moors—quite a new race of town
dwellers, which may be said to have absorbed all others.
Whereas the population of the interior of the country to a great
extent escaped intermixture with the new elements, up to the time of
the arrival of the Arabs, it has been quite otherwise in the towns,
where foreign traders settled and intermingled with the native
inhabitants.
Amongst the Moors in the towns are found, as has been said, the
so-called “Andaluz,” who were driven out of Spain. Several of these
distinguished families have carefully preserved the records of their
genealogy, and some of them still possess the keys of their houses
in Seville and Granada. They have certainly intermarried with other
families of different origin, but still cling to their traditions, and retain
and exercise to a certain extent the handicrafts and occupations of
their forefathers in Spain. The gardeners of “Teburka,” for instance,
are descendants of the gardeners of the Guadalquivir, and the
forefathers of the potters near Nebel were potters at Malaga.
The blood of slaves of all nationalities has also been introduced
into the people known as Moors.
The complexion of the Moor is fair, or, more rarely, olive; it
resembles that of the Southern Italian or Spaniard. The shape of the
head is oval the nose long, and they have thick eyebrows and very
black beards. Of medium height, they are well built, and their
carriage is easy and graceful. They are considered more honourable
than either Jews or Christians, and were noted formerly for their kind
treatment of their slaves. Though clever workmen and well educated,
their moral tone is not high. In old days the town of Tunis was the
great market frequented by the people of the Sudan; nothing was
considered worth having that had not been made by a Tunisian.
The Turkish element, as represented by the Bey and his
surroundings, has long since ceased to have any influence on the
Moorish race in Tunisia. No real Turks are now to be found in the
country. In the towns, however, are a few descendants of Turkish
soldiers and Tunisian women; they are called “Kurughis,” and are
lazy, vain, and ignorant, and consequently not much respected.
The Moors, or the town dwellers, on the whole, are, however, not
so vigorous and energetic as the nomads and the mountaineers;
their manners are more effeminate, and they are lazier.
Crimes against the person, such as assault or murder, are rare in
the towns, but drunkenness on the sly is common, and immorality is
prevalent.
The Jews.
The ancient conquerors of the country, the Carthaginians and
Romans, who covered it with towns, forts, and monuments, have left
no impress of themselves on the appearance of the present
inhabitants, nor do there survive amongst the tribes any traditions
concerning them.
No more remains to recall the Vandals and Goths, yet the latest
researches prove the existence in early days of other Semitic
peoples besides the Arab.
The earliest importation to the country of Semitic blood was
doubtless the Phœnician. To this is due the fact that many of the
types portrayed on Chaldaic and Assyrian ruins are now found
scattered throughout Tunisia.
At the same time as the Phœnicians may be mentioned the Jews,
the earliest of whom probably came to Barbary at the same time as
the former, but their number was largely added to later, after the
conquest of Jerusalem by Titus. Moreover, it is known that many
Berber tribes were converted to Judaism and remained Jews, even
after the Arab conquest. The classic type of European Jew is
therefore rarely met with in Tunisia.
After the Mohammedans the Jews are, numerically, most strongly
represented in Barbary. They form somewhat important
communities, not only in the town of Tunis, but also in all other
towns, even in the island of Jerba. Possibly with theirs has mingled
the blood of the ancient Carthaginians.
There are also a great number of Jews whose ancestors were
ejected from Spain and Portugal; these are called “Grana,” from their
former most important trading city in Spain.
These “Grana” were under the protection of the foreign consuls,
and therefore have had nothing to complain of; but the old Jews
were in a disastrous condition in former days, and suffered much, so
much that some isolated families abjured Judaism and became
Mohammedans; such they are still, but they always associate with
their former co-religionists. Other Jews—those of Jerba, for instance
—have modified their religious forms, pray to Mohammedan saints,
and hold their Marabouts in honour.
A peculiar head-dress distinguishes those Jews who are under no
protection, from those who are protected by the consuls. It is an
irony of fate that many Jews have placed themselves under Spanish
protection, because they knew that Spain was their home in old
days. Now they are protected by the country that formerly drove
them forth. Somewhat similar is the case of the Algerian Jews in
Tunis who seek French protection.
All the Jews of Tunis retain the ancient Spanish ritual. They are
peaceful and well behaved, and not so grasping as others of their
faith, but they are clever at taking advantage of a good opportunity
when there is a prospect of making money, or when their trade may
be extended. Commerce is therefore in great measure in their
hands.
In the whole Regency of Tunisia there are over fifty thousand
Jews, and their numbers increase rapidly. In the town of Tunis there
is a “ghetto,” the quarter formerly devoted to them, and where they
were compelled to dwell. It has long since become too small, and the
Jews have now spread over all the other quarters, and in the
bazaars have wrested from the Moors many of their shops.
This Jewish community is an interesting study, and one is
astonished to find how in many respects they so little resemble their
co-religionists in other countries.
COSTUMES
The Dress of the Countrywomen (Arabs—
Berbers)
Over the whole of Tunisia the countrywomen, whether Arab or

Berber, wear a similar costume, which must be almost identical with
that worn by the Grecian women in olden days.
The dress of the women of ancient Greece consisted of what was
known as the “peplos”[8] (πέπλος), a white wrapper gathered in by a
belt about the waist (ζώνη), and supported on the shoulders by pins
(περόναι and ἐνεται). As head-dress, or for ornament, they wore a
kind of forehead band (χρήδεμνον) or veil, and, in addition to these,
earrings, necklets, bracelets, etc. etc.
The “peplos” was a large piece of stuff without seam, which was
folded round the body from one side.
The dress of a Tunisian woman of to-day is the same. It consists
of a “m’lhalfa,” which resembles the “peplos,” being a long narrow
piece of stuff, wound round the body in such a manner that it entirely
covers the back and shoulders. One end is brought over the breast,
and hangs down in front; the other end covers the lower limbs, and
forms a skirt. The piece is so long that it hangs in folds, which partly
conceal the sides. Whilst the Greek “peplos” was held together by
“fibulæ” on the shoulders, the clasps that confine the “m’lhalfa” are
placed rather forward—over the breast. The Grecian woman’s neck
was bare, her chest covered. But it is the contrary with the Tunisian
woman. In other words, the “m’lhalfa” is merely a “peplos” which has
been drawn forward. Many Tunisian women draw the “m’lhalfa” over
the breast, and arrange one end to form a full drapery; others, as in
the Matmata villages, omit this, but wear over their bosom a thin
square of stuff called “katfia.” This is secured by the clasps already
mentioned.
In a few places, such as the Khrumir mountains, the “m’lhalfa” is
composed of two pieces of stuff worn one in front and one behind,
held together by the breast clasp. Over the neck and shoulders is
laid a rather large towel. The “m’lhalfa” is always bound in at the
waist by a long woollen belt, generally white or of some bright colour.
The clothes for daily wear are, as a rule, of a dark blue woollen
material, but for festivals or weddings they wear red, yellow, or parti-
coloured garments of silk, cotton, or wool.
In most regions a kerchief is worn on the head (tadchira); round
this is wound a turban (assaba), composed of a long piece of stuff
ornamented with coins or trinkets. Over this again is thrown a large,
often embroidered, cloth, in which the face is enveloped (begnuk).
Generally speaking, the Tunisian women wear no underclothing,
at all events not in daily life in the country. On festive occasions,
especially in the towns of the oases, they assume a white shirt
(suïera). It has very short or no sleeves. A bride, as a rule, wears
one. The bridal shirt (gomedj) is generally embroidered about the
opening at the neck in silk or cotton, in stripes of black, yellow, blue,
and red.
In daily life they do not wear shoes, but go barefoot. At the feasts
the women put on yellow shoes without heels (balgha).
The ornaments worn by the poor are mostly of brass, copper, or
horn; by those in better circumstances, of silver; or sometimes by the
rich, of gold.
Round the neck are worn strings of glass beads, and in the ears
large slight earrings (“khoras,” from cross); on the wrists, broad open
bracelets (addide). Finally, they wear large heavy anklets called
“kralkral,” that are generally made not to meet.
To fasten the “m’lhalfa” on the shoulders large brooches are
commonly employed. These are in the form of an open circle,
through which passes a pin (khlel).
On the breast they wear a silver chain (ghomra), from which
depend coins or flat plates of metal. These chains are fastened to
the breast-pins. All these ornaments are made by the Jews of the
towns or oases, and are really artistic productions.
The women do not usually wear straw hats, though some may
amongst the Berbers of the island of Jerba. These hats are precisely
similar to those depicted on some of the Tanagra figures found in
Greece.
In Jerba are worn crescent-shaped breast ornaments, said to
come from Tripoli; also ornaments in filagree work from Zarsis.
The women often carry a little looking-glass tied to their breast-
pins, and also the requisites for applying henna and kohol.
When they fetch water in their great pitchers they carry these
slung on their backs by means of a wide band round the forehead, or
in the end of their turban, loosened for the purpose.
Their hair is never plaited, but is covered by the cloth or turban. A
woman is rarely seen in stockings. In a few places where the roads
are bad they wear wooden shoes. The Khrumirs are proficient in
making these.
Much of the material employed in the women’s dress is woven or
made by themselves in the region in which it is worn, but some is
brought from Tripoli, the Sudan, or from Europe. As a rule, however,
the countrywomen wear only their own handiwork.
In the Matmata mountains and the neighbouring oases I was able
to collect and buy a complete costume, the whole of which had been
made in that region, and chiefly of native materials.
It must be mentioned that the Berber women have everywhere
more freedom than their Arab sisters, and are therefore often
unveiled. Yet many of the tribes have gradually adopted Arab
customs, and in this particular follow their example—at all events in
the vicinity of a town, for in the country the women all go unveiled,
only hiding their faces on occasion.
We will now examine the dress of the men, both Arabs and
Berbers.
In contradistinction to the Kabail of Algeria, the Arabs always
cover their heads. In Tunis, where the races are so mixed, nearly all
the men go covered. They wear white cotton caps under the red
“shashia,” allowing a narrow edge of white to appear beneath the
latter.
The Arabs always wear a haik or burnous; the Berbers, generally.
The burnous, as is known, consists of a cape united at the breast.
The “haik” is a piece of thinner stuff, which is worn as a drapery,
usually under the burnous, but also alone.
In the southern mountains of Tunisia I found that many of the
mountaineers wore, instead of burnous or haik, a piece of stuff
without hood or seam. In this they draped themselves so that the
head was covered. It was usually of brown or grey wool. The
burnous is as a rule white, as is also the haik. Many of the poorer
folk, especially amongst the Berbers, wear nothing else in daily life;
but they assume a shirt, waistcoat, and coat, as also a gala burnous
(sjebba) on festive occasions. This last is shorter than the real
burnous, and is made with short wide sleeves, of bright coloured
stuff, often embroidered in silk.
The people on the coast near Susa and to the south have a still
shorter brown-hooded garment in place of a haik or burnous, and
they wear trousers. This costume is convenient for fishermen.
A large broad-brimmed straw hat is worn by the denizens of the
plains. Shoes or sandals of morocco leather or hide are worn by
many.
Red morocco leather boots, worn inside a shoe, are used by
riders, also spurs.
The purse is a long, narrow, knitted or woven bag.
The Berber often wears a shirt, and, in such cases, only a haik
over it, and no burnous.
The usual costume of the Arab is that worn in Algeria—the
burnous and the haik, the latter bound on with a camel’s-hair cord;
shoes (or boots). Of the Berber, shirt, haik, burnous, bare legs, and
uncovered head.
Such variations of these costumes as may exist in Tunisia have
been brought about by an altered mode of life and the admixture of
races.
Dr. Bertholon declares that most of the costumes are of very
ancient origin. That of the Jews, for instance, he dates back to the
days of the Carthaginians; the burnous, he says, resembles the
hooded Roman cloak.
The Moorish woman’s dress is very pretty, but extremely
coquettish. It is overladen with ornaments.
“In the morning she wears a very scanty costume. If one has the
luck to catch a glimpse of her at an early hour as she moves hither
and thither in the harem, she is not easily forgotten. She is clad in a
simple shirt, with short sleeves, which leave her plump arms
exposed. Under this she wears trousers, so short that they scarcely
reach the knees; a little shawl, of which the ends are knotted in front
at the waist, replaces a skirt, and enfolds her pretty form. Her
bosoms are supported by a narrow bodice, and about her hair is
bound a silk kerchief, but her locks fall down over her neck” (Des
Godins de Souhesnes).
When she leaves the house she wears a “gandura,” a kind of
cloak of transparent material, fastened on the shoulders by gold or
silver pins. Besides this she has put on wrinkled white linen trousers
reaching to her ankles; over her head she throws a white kerchief;
and, lastly, she conceals her face with a long embroidered veil.
The Moorish woman blackens her eyebrows, enhances the
beauty of her eyes with antimony (khol), and stains with orange-red
henna the nails of her fingers and toes and the palms of her hands.
The dress of the Moor much resembles that of the Jew. He wears
a tasselled cap (shashia), surrounded by a turban, and a silken vest
or coat, embroidered in gold or silver.
The trousers are very wide, and fall in heavy folds; the lower part
of the leg is uncovered, and on his bare feet he wears broad shoes
of red or yellow morocco leather (babush).
The costume of the Jews, as worn by them before they were free,
to distinguish them from the Arabs, is very picturesque, and,
fortunately, still universal.
The men, who are generally handsome, wear a tasselled shashia,
often surrounded by a turban. Their wide, pleated Turkish trousers
reach a little below the knee, and are secured at the waist by a belt.
They wear also coat and waistcoat, stockings, and shoes.
Many have now adopted European attire, but the characteristic
Jewish type is easily distinguished.
The Jewish women are not veiled. They wear shirts, narrow
embroidered silk trousers, cotton stockings, shoes, and on their
heads a pointed cap.
These women, when young, are very pretty, but also very
immoral. They are generally spoilt by being too stout, young girls
being fed up to make them attractive for their wedding.
There is no native industry peculiar to Tunisia, but there are a few
which may be considered worth notice.
The holy town of Kairwan is famed for its beautiful carpets. In
Gefsa and Jerba also curious and beautiful carpets are woven.
Clay ware is a speciality of Nebel, where, to this day, pottery is
made that recalls that found in the Phœnician and Roman tombs
near Carthage. Pottery is also made at Jerba in the form of jars,
vases, etc., which are sent to different parts of the country—northern
Tunisia obtaining its pottery from Nebel; southern, from Jerba.
Amongst the tribes, pottery is also made by the women and
negresses, but generally without the aid of the potter’s wheel. The
Khrumir in particular are noted for their peculiar ornamented pottery.
In the towns, moreover, and especially in Tunis, there are
numbers of shoemakers, leather workers, saddlers, harness and
pouch makers, etc. etc. There are also excellent dyers and makers
of perfumes.
In the oases are made fans, and baskets of palm leaves and of
alfa straw; baskets, hats, and great crates for corn, which take the
place in these regions of the clay jars of the Kabail.
Tripoli lies quite close to Tunis, and there manufactures attain a
high level; a great quantity therefore of stuffs—carpets and worked
leather articles—are imported thence. The Jews are the goldsmiths,
and, even in the interior and in the southern oases, possess the art
of making pretty bracelets and ornaments.
The inhabitants of Zarsis are renowned for their peculiar filigree
work.
POSTSCRIPT
The information adjoined regarding the number of souls included in

each of the Berber tribes, and of their domestic animals, came to
hand only after the first portion of my book had gone to press. I
therefore add it here. This information has been collected with great
pains throughout the Government of El Arad by the kindly help of M.
Destailleur, Contrôleur Civil to that Government. It is positively
reliable, the calculations which I was able to make in person during
my stay in several of the villages, with the same view, corresponding
exactly to those in the table. Only—as an outsider—I must aver that
the number of horses may not be quite correct, but for some places
appears computed too low. As for instance in Hadeij, where, it is
said, none are to be found, which was certainly not the case.
Possibly the explanation may be that the sheikhs feared that the
inquiry made by the Government arose from a desire to know how
many mounted men this tribe could place in the field in time of war.
Number of Sheep and
Names of Tribes and Villages. Asses. Oxen. Horses. Camels. Mules
Inhabitants. Goats.
Jara 1925 500 40 100 40 700 40
Menzel 2200 600 60 35 40 410 90
Shenini 1040 300 2 25 30 185 30
Ghenush 350 100 4 3 8 200 40
Bu Shma 50 20 10 30
Udref 750 280 70 8 120 450 2
Metuia 1800 200 20 10 100 600 60
Tebulbu 235 45 25 4 38 350 1
Zarat 165 45 55 3 12 1000
Ghraïra 450 100 8 390 1450
Alaia 232 30 20 351
Hazem 1229 210 4 36 240 2880
Hamernas 2100 600 57 37 300 2100 1
⎧ Gassur 900 140 70 20 50 350 10
⎪ Debdaba 1390 115 22 40 92 520 19
⎪ El Begla 1455 432 41 535 1830
Beni-Zider, ⎪ Shelahsha 1689 400 95 1400 10,000 4
South of ⎨
Matmata 1000 120 8 20 400 1800
the Shott. ⎪
⎪ Shehel 1100 150 25 1200 2500
⎪ El Heurja 1000 140 30 420 2000
⎩ Zauia 868 320 35 800 8000 4
Tujud 210 15 30 2 55 520
⎧
Zarua 604 55 27 1 207 713 2
⎪
⎪ Dehibat 100 20 3 2 50 1000
⎪ Ben Aissa 340 25 25 3 65 311
⎪ Guelaa Ben Aissa 495 40 45 3 115 410
Matmata
⎨ Smerten 105 10 1 25 265
Mountains.
⎪ Beni Sultan 632 43 73 1 55 200 2
⎪ Tujan 1071 51 80 3 169 1000 1
⎪ Uled-Sliman-Hadeij 1300 200 200 300 2700 8
⎪
Lasheish 1020 120 223 6 263 2036 2
⎩
Tamezred 1082 50 100 7 400 4600 4
Urghamma. ⎧ Neffat 3830 826 46 221 3371 9926 3
⎪ Accara 5496 750 250 110 1335 6060
⎪ Tuasin 2461 1203 15 600 6945 15,263
⎪ Khezur 3411 890 150 142 1353 9745
⎪
Ghomrasen 1376 565 3 43 684 2848
⎪
Shenini-Duirat 410 80 20 3 300 1960 1
⎪
⎪ Guermasa 460 80 30 8 170 1150
⎪ Uderma. ⎧ Hamidia 287 60 25 255 890
⎪ ⎨ Uled-Debab 389 150 20 200 2000
⎨ ⎩
⎨ of Tribes and
⎩ Villages. Number of Sheep and
Names Asses. Oxen. Horses. Camels. Mules
⎪ Inhabitants. Goats.
⎪ Deghagha 585 250 10 34 300 300
⎪ Uled Shada 330 125 42 320 1200
⎪ Suabria-Duirat 153 7 2 2 32 800
⎪ Beni Barka 125 25 7 2 60 240
⎪ Zedra 117 25 12 1 14 360
⎪ Gatufa 130 30 15 4 11 400
⎪
⎧ Uled-Lazareg
⎪
Jelidat ⎨ Uled-Aun 302 100 4 50 300 1100
⎩
⎩ Uled-Ashiri
Quadid 125 30 4 4 80 600
Duiri 1357 63 54 10 280 3400

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Transition Metal-Catalyzed Pyridine

Synthesis. Transition Metal-Catalyzed

Transition metal catalyzed furans synthesis :

Transition Metal-Catalyzed Benzofuran Synthesis Xiao-

Transition Metal Catalyzed Pyrimidine, Pyrazine,

Synthesis and Modification of Heterocycles by Metal

Spectral Methods in Transition Metal Complexes 1st

Two Dimensional Transition Metal Dichalcogenides 1st

Handbook of transition metal polymerization catalysts

Coherent Light-Matter Interactions in Monolayer

AMSTERDAM • BOSTON • HEIDELBERG • LONDON

British Library Cataloguing-in-Publication Data

For Information on all Elsevier Publishing

Dedicated to my wife, children, and my parents

Scheme 1.1 Selected examples of bio-active pyridine derivatives.

Transition Metal-Catalyzed Pyridine Synthesis. DOI: http://dx.doi.org/10.1016/B978-0-12-809379-5.00001-9

Scheme 1.1 (Continued)

Intramolecular cyclization of substrates to the corresponding pyridine

Transition Metal-Catalyzed Pyridine Synthesis. DOI: http://dx.doi.org/10.1016/B978-0-12-809379-5.00002-0

Scheme 2.1 CuBr-catalyzed pyridines synthesis from N-propargylic β-enaminones.

A procedure by using enamino ester and alkynone as the substrates

Scheme 2.2 Pd-catalyzed pyridines synthesis from N-(2-bromoallyl)-N-cinnamyltosylamides.

In 2014, Gagosz and coworkers reported their achievement on gold-

Scheme 2.3 Au-catalyzed pyridines synthesis from azirines.

Eastgate and coworkers developed a Ni-catalyzed C-H functionali-

O N N NH2 Piv 2O (1 equiv.), toluene O N N NH2

Scheme 2.4 Ni-catalyzed synthesis of JAK2 inhibitor BMS-911543.

Reddy’s group reported a silver-catalyzed annulation of enynyl

Scheme 2.5 Ag-mediated synthesis of pyridines from enynyl azides.

A Lewis acid mediated reaction of acyclic vinyl allenes and imines

hydrogenation using cyclohexene as hydrogen donor in good yield

Scheme 2.6 Pd/C-catalyzed synthesis of pyridines from tetrahydropyridines.

Movassaghi and Hill developed a ruthenium-catalyzed cycloisomeri-

20-mL portion of dichloromethane. This solution was concentrated under

Scheme 2.7 Ru-catalyzed synthesis of pyridines from 3-azadienynes.

Hanzawa, Saito, and their coworkers developed a rhodium(I)-cata-

Scheme 2.8 Rh-catalyzed synthesis of pyridines from σ-alkynyl-vinyl oximes.

Zhang and Gao studied the silver(I)-catalyzed cyclization reaction

Scheme 2.9 Ag/Au-catalyzed synthesis of pyridines from oximes.

Park and coworkers developed a highly efficient procedure for the

purified by flash column chromatography using hexane : ethyl acetate

Scheme 2.10 Rh-catalyzed synthesis of pyridines from diazo compounds.

More recently, a visible-light-promoted cyclization of acyl oximes to

Scheme 2.11 Light-promoted synthesis of pyridines from acyl oximes.

Additionally, the intramolecular cyclization of diyne-cyanohydrin

CoI2(dppe) (5 mol%), 80°C

Zn (2.75 equiv.), CH3CN (3.0 mL) N

Scheme 2.12 Cobalt-catalyzed synthesis of pyridines from nitrilediynes.

Rhodium catalysts were applied in this type of transformation as

Scheme 2.13 Rh-catalyzed synthesis of pyridines from nitrilediynes.

3.1 SYNTHESIZED BY [2 1 2 1 2] CYCLIZATION REACTIONS

Heller and coworkers performed cobalt-catalyzed photochemical syn-

pure 2,20 -dicyano-1,10 -binaphthyl with 1,6-heptadiyne, 1,7-octadiyne,

Scheme 3.1 Co-catalyzed synthesis of 3- or 4-aminopyridines.

Saá and coworkers reported a one-step procedure for the synthesis of

Scheme 3.2 Co-catalyzed synthesis of spiropyridines.

In 2008, Schreiber’s group studied the cycloaddition of silyl-

inhibitor of the neuregulin/ErbB 4-dependent signaling pathway

Scheme 3.3 Co-catalyzed synthesis of silylated pyridines.

In the same year, Deiters and coworkers developed an approach for

CEM Discover microwave synthesizer at 300 W. After cooling, the reac-

CpCo(CO)2 (10 mol%) R

DDQ (1.2 equiv.)