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Regioselective Radical Cascade Cyclizations of Alkyne-Tethered

Cyclohexadienones with Chalcogenides under Visible-Light
Catalysis
Vadla Shiva Prasad, Vadithya Ranga Rao, Maram Gangadhar, Sunil Kumar Nechipadappu,
and Praveen Reddy Adiyala*
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sı Supporting Information
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ABSTRACT: Herein, we demonstrated a silver/K2S2O8-mediated

highly regio- and diastereoselective 6/5-exo trig radical cascade
cyclization of alkyne-tethered cyclohexadienones with sulfonyl
hydrazides or sodium sulfinates and subsequent selenation to access
6,6-dihydrochromenone and 6,5-fused tetrahydro benzofuranone
derivatives. This reaction protocol features high functional group
compatibility and has a wide substrate scope providing a variety of
dihydrochromenones and tetrahydro benzofuranone derivatives in
good to excellent yields. The reaction proceeds via the attack of a
sulfonyl radical to alkyne over the activated Michael acceptor. The
TEMPO quenching experiment implies the presence of a radical
intermediate. Further synthetic versatility of 6,6- and 5,6-fused
derivatives is also showcased.

■ INTRODUCTION
Organochalcogen compounds,1 particularly containing sulfon-
yl2 (R1SO2−) and seleno3 (R2Se−) groups, are highly versatile
functional groups that are widely present in natural products
and4 pharmaceuticals and play a substantial role in organic
synthesis (nucleophiles, electrophiles, ligands, and catalysts),
biochemistry,5 medicinal chemistry,6 and materials science.7
Additionally, molecules containing selenium and sulfone have
been widely used in organic synthesis.8 The C−S and C−Se
bonds are weak, making it simple to add, delete, and change
them into different functional groups. The incorporation of
chalcogen functionality into a single molecule might provide an
opportunity to enhance the bioactivity of the drugs or original
lead compounds.9 Therefore, the discovery of novel techniques
for incorporating both seleno and sulfonyl groups into a single
molecule is of enormous synthetic significance, enabling a
rapid increase in molecular complexity.
Visible-light photocatalysis10 has emerged as a key method
for stimulating a variety of synthetic conversions for the
creation of C−X and C−C bonds in the quest for energy-
efficient and sustainable synthesis. For the production of
radical ion intermediates under benign conditions, visible light-
induced catalysis has proven to be one of the most reliable
methods. On the other hand, the radical cascade cyclizations11
are privileged strategies that have been rapidly applied for the
manufacture of complex molecular skeletons from commer-
cially available acyclic substrates. In particular, the cascade
cyclizations of 1,6-enynes12 have drawn a lot of attention for
© 2023 The Authors. Published by
American Chemical Society
35809
manufacturing of cyclic complex ring systems from acyclic
moieties. Alkyne-tethered cyclohexadienones are used in
manufacturing cyclic complex ring systems from acyclic
moieties. Alkyne-tethered cyclohexadienones, which can be
obtained by dearomatizing the appropriate phenols, are
annulated in a variety of ways and are able to generate novel
cyclic structural entities. In this context, the production of
fused carbocycles from alkyne-tethered cyclohexadienones has
received substantial research attention.13 As a result, great
efforts have been made to synthesize these fused carbocycle
motifs in a simple and effective synthetic approach. Although
several strategies have been developed to construct decorated
bicyclic frameworks via cyclizations of cyclohexadienones,
recognized as powerful strategies, these structural entities are
widely found in bioactive natural products. For instance, metal
catalysts including Rh,14 Pd,15 Cu,16 and Ni17 have been
widely studied in the synthesis of 5- and 6-fused carbocycles.
There are only a few reports on the radical cascade cyclization
of alkyne-tethered cyclohexadienones for the formation of 6,5-
and 6,6-fused carbocycles. In a pioneering report, Lam and co-
Received: May 15, 2023
Accepted: September 7, 2023
Published: September 20, 2023
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Scheme 1. Comparative Approaches for Cascade Cyclizations of Alkyne-Tethered Cyclohexadienones between the Reported
Work and This Work
workers developed a radical cascade cyclization of alkyne-
tethered cyclohexadienones with sulfonyl radicals produced
from sulfonyl azides (Scheme 1,A)18 under visible light-
induced iridium photocatalysis. Volla and co-workers demon-
strated a Giese-type cyclization protocol for the highly
diastereoselective synthesis of sulfenylated dihydrochrome-
nones under visible-light irradiation (Scheme 1,B).19 Sahoo’s
group also discovered a novel protocol for the construction of
3-thioaryl-bearing fused dihydrochromenones via regio- and
chemoselective radical cyclization under N-hydroxyphthali-
mide (NHPI) catalysis (Scheme 1,B).20 Later, Xu developed a
three-component tandem cyclization/substitution for the
construction of highly substituted dihydrochromenones using
cyclohexadienones, diselenides, and H2O (Scheme 1,C).21 Xu
and colleagues reported the cascade cyclization of alkyne-
tethered cyclohexadienones, although they employed a
presynthesized starting material where the preparation
required reflux temperature and a pricey hypervalent reagent
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Article
(Scheme 1,D).22 Very recently, while this manuscript was
under preparation, Volla and co-workers also demonstrated a
multicomponent radical cascade reaction for the synthesis of
highly functionalized dihydrochromenones using explosive
aryldiazonium salts as aryl partners and expensive DABSO as
a SO2 source and also as a redox mediator under reflux
conditions (Scheme 1,D).22,23
Inspired by these results and our previous experience on
photoredox catalysis,24 we envisioned that sulfonyl radicals
generated from sulfonyl hydrazides or sodium sulfinates might
be added to alkynyl cyclohexadienones and undergo Giese-
type cyclization, followed by selenation by diselenides to
produce bis-functionalization (Scheme 1,E) (see Scheme 1).
■ RESULTS AND DISCUSSION
To test the above hypothesis, we commenced our study to
investigate the optimal reaction conditions (see Supporting
Information Table S1). Under the optimized reaction
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Scheme 2. Substrate Scope of 6-Exo Trig Radical Cascade Cyclization of Cyclohexadienonesa

a
Standard Condition for 6-Exo Trig Cyclization: Internal alkyne (1.0 equiv), hydrazide (1.0 equiv), diphenyl diselenide (0.5 equiv), and Ag2CO3
(1.0 equiv) were mixed in 2 mL ACN under an inert atmosphere with 5 W blue LED irradiation.

conditions in hand, we turned our attention to probing the
versatility of the developed protocol by independently
screening with various cyclohexadienones, sulfonyl sources,
and diaryl chalcogens (Scheme 2). First, the electronic effect of
substituent R1 on the cyclohexadienones was investigated.
Gratifyingly, both electron-withdrawing and -donating sub-
stituted arenes at the alkyne terminus of cyclohexadienones
were well tolerated in this transformation and afforded the
corresponding 6-exo trig cyclized products in good to excellent
yields and with high diastereoselectivity, which indicated that
electronic effects are not much effective in this protocol
(Scheme 2,4a−e). We then examined the reaction efficiency
with the replacement of arene at the alkyne terminus of
cyclohexadienones with hetero aryl as well as alkyl substituent
under the standard reaction conditions; the reaction proceeded
well to afford the corresponding desired products in excellent
35811
yields (Scheme 2, 4f−g). Changing the substituent in the
quaternary carbon of cyclohexadienones from methyl to iso-
propyl or phenyl made the 6-exo trig transformation proceed
smoothly and gave the desired products in good yields
(Scheme 2, 4h−i). The radical cascade cyclization is also
feasible for the cyclohexadienone having a methyl moiety at
the α-position of carbonyl, affording the 6-exo trig cyclized
product in an excellent yield (Scheme 2, 4j). Encouraged by
these results, we were devoted to searching for the versatility of
this present protocol to further extend the substrate scope with
respect to diaryldiselenides.
Delectably, electron-withdrawing and -donating groups were
well tolerated at the ortho, para, and meta positions of the
phenyl ring of diaryl diselenides, affording the desired cyclized
products in good to excellent yields (Scheme 2, 4k−o).
Notably, heteroaromatic-substituted diaryl diselenides under-
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Figure 1. Crystal X-ray diffraction analysis of 4a, 4g, and 6a.

Scheme 3. Substrate Scope of 5-Exo Trig Radical Cascade Cyclization of Cyclohexadienonesa

a
Standard Condition for 5-Exo Trig Cyclization: Terminal alkyne (1.0 equiv), sodium phenyl sulfinate (3.0 equiv), diphenyldiselenide (0.5 equiv),
and K2S2O8 (2.0 equiv) were mixed in 2 mL of ACN under an inert atmosphere with 5 W blue LED irradiation.

went this transformation and afforded the corresponding 6-exo
trig product in a good yield (Scheme 2, 4p). Furthermore,
various sulfonyl hydrazides such as 4-methylphenyl and
cyclopropyl sulfonyl hydrazides were also compatible with
this catalytic system, leading to the expected 6-exo trig cyclized
products 4r in excellent yields (Scheme 2, 4q−s). We also
further examined the performance of reaction efficiency with
ortho-substituted arene at the alkyne terminus of cyclo-
hexadienone, and it was observed that the formation of the
desired product in a good yield (Scheme 2, 4t), and it
indicated there is no steric effect on this transformation. The
35812
addition of the aryl sulfonyl group occurred from the less
sterically hindered exo side, and it is important to note that all
of the products were produced as single diastereomers. Crystal
X-ray diffraction analysis of 4a and 4g (Figure 1) indicates a
clear relationship between all the stereocenters. However, the
aliphatic selenides fail to give the desired product due to the
low stability of the methyl selenide radical (Scheme 2, 4u).
Next, we then investigated the scope of developed radical
cascade cyclization with a variety of cyclohexadienones having
terminal alkynes, sodium arylsulfinates, and diaryldiselenides in
the presence of K2S2O8 under blue LED light irradiation (see
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Scheme 4. Gram-Scale Reaction and Synthetic Utility of 6/5-Exo Trig Radical Cascade Cyclization of Cyclohexadienones

Supporting Information Table S1). Our assumption was Scheme 5. Control Experiments
expected to be a 6-exo-trig cyclized product similar to internal
alkynes, but the reaction surprisingly afforded the 5-exo-trig
cyclized product as depicted in Scheme 3. The absolute
structure of 6a was further confirmed with crystal X-ray
diffraction analysis (Figure 1). Next, we explored the substrate
scope with respect to various diaryl diselenides. Both electron
donating as well as withdrawing groups bearing the phenyl ring
of diaryl diselenides underwent this 5-exo-trig cyclization and
we observed the desired products in good to excellent yields as
well as excellent diastereoselective (Scheme 3, 6a−f). Notably,
meta halo substituted diaryl diselenides gave the product 6d in
good yield (78%) with a dr of 7:3.
Later, sodium arylsulfinates having functionalities such as 4-
chlorophenyl and cyclopropyl were also tested to check the
reaction efficiency, and the reaction proceeded well to afford Scheme 6. Plausible Mechanism
the desired 5-exo-trig products in excellent yields (Schemes 3,
6g−h). The reaction also proceeded with cyclohexadienone
having a methyl moiety at the α-position of carbonyl, affording
the 5-exo-trig-cyclized product in an excellent yield (Scheme 3,
6j). Notably, 1,2-bis(2-fluorophenyl)diselane underwent 5-exo
trig transformation smoothly and afforded the desired product
in a good yield (Schemes 3, 6k). Aliphatic selenide failed to
give the desired product (Schemes 3, 6l).
To demonstrate the synthetic utility further, a gram-scale
reaction for the synthesis of 4a and 6i is carried out, as
illustrated in Scheme 4. Internal alkyne (0.500 g, 1.0 equiv)
and terminal alkyne (0.500 g, 1.0 equiv) were both subjected
to this transformation and afforded the required products 4a
and 6i in 85 and 91% yields, respectively. When chalcogenated
dihydrochromenones 4a and tetrahydrobenzofuranones 6i
were individually treated to react with m-CPBA, they generated
deselenated products 7 and 8 in 75 and 80% yields,
respectively (please see the Supporting Information).
The reaction was carried out in the presence of the radical
scavenger TEMPO (1.0 equiv) under optimal reaction
circumstances to ensure the involvement of the radical
pathway for both 5/6-exo trig cyclizations (Scheme 5). A
trace amount of the desired product was observed. This result
indicates that this reaction possibly proceeds through a radical
pathway.
Based on the control experiments and previous literature,25 a
plausible mechanism of the present method for 6/5-exo-trig
cyclization is shown in Scheme 6.
Initially, the interaction of sulfonyl hydrazide with Ag2CO3
produced the highly active species Ts•. The sulfonyl radical
species was added to the internal alkyne of cyclohexadienones
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to give alkenyl radical II, which underwent an intramolecular
Giese-type 6-exo trig cyclization, furnishing the α-carbonyl
radical intermediate IV. Furthermore, the stereoselective attack
of the aryl selenyl radical onto the intermediate IV generated
the final product 4 (The stereoselective attack of aryl selenium
is explained in the Supporting Information). Similarly, in the
case of terminal alkyne-tethered cyclohexadienones, sulfonyl
radicals were generated from sodium sulfonates, and further,
this sulfonyl radical species was added to the terminal alkyne of
cyclohexadienones to give alkenyl radical I, which underwent
an intramolecular Giese-type 5-exo trig cyclization, furnishing
the α-carbonyl radical intermediate III. Further, the radical
cross-coupling of intermediate III and the aryl selenyl radical
that was formed by homolytic cleavage of diaryl diselenide in
the presence of light generated the final product 6.
In conclusion, highly functionalized fused chalcogenated
dihydrochromenones and tetrahydrobenzofuranones have
been developed via silver/K2S2O8-mediated highly regio- and
diastereoselective 6/5 exo-trig radical cascade cyclization of
alkyne-tethered cyclohexadienones sulfonylhydrazides/arylsul-
finates and diselenides under visible-light irradiation. The
reaction displayed good functional group tolerance for a wide
variety of functional groups and proceeded under the radical
mechanism and mild conditions, employing cheap and easily
available Ag2CO3 and K2S2O8 as an additive and an oxidant,
respectively. Initial mechanistic research supported a radical
route. In addition, we also demonstrated the deselenation of
dihydrochromenones and tetrahydrobenzofuranones using m-
CPBA. Further studies on the enantiomeric radical cascade
cyclization under visible-light catalysis are underway in our
laboratory and will be disclosed in due course.
■ EXPERIMENTAL SECTION
General Information. Unless otherwise noted, all the
commercial materials were used without further purification.
All reactions were performed under an inert atmosphere and in
oven-dried glassware with magnetic stirring. All solvents were
dried before use following the standard procedures. Reactions
were monitored by TLC on precoated silica gel 60 F-254. TLC
plates were visualized with UV light (254 nm), iodine
treatment, or p-anisaldehyde stain. Column chromatography
was carried out using silica gel (60−120 and 100−200 mesh)
packed in glass columns. NMR spectra were recorded at 300,
400, and 500 MHz (H) and at 75, 100, and 125 MHz (C),
respectively. Chemical shifts (δ) are reported in ppm, using the
residual solvent peak in CDCl3 (H: δ = 7.26 and C: δ = 77.00
ppm) as the internal standard, and coupling constants (J) are
given in Hz. HRMS were recorded using ESI-TOF techniques.
General Procedure for the Cascade 6-Exo Trig
Cyclization of Alkyne-Tethered Cyclohexadienones (i).
In an oven-dried glass vial, internal alkyne (0.05 g, 1.0 equiv),
hydrazide (0.039 g, 1.0 equiv), diphenyldiselenide (0.032 g, 0.5
equiv), and Ag2CO3 (0.057 g, 1.0 equiv) were dissolved in 2
mL ACN; the vial was then sealed with a PTFE septum and
purged with argon. The reaction mixture was stirred
continuously for 6 h while being exposed to 5 W blue LED
light at room temperature. Then, the reaction mixture was
diluted with water. It was extracted with ethyl acetate (3 × 10
mL). Then, to the organic layer was added Na2SO4, and the
mixture was concentrated under reduced pressure. The residue
was directly subjected to flash chromatography on silica gel
(hexane/ethyl acetate) to afford the desired product.
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General Procedure for the Cascade 5-Exo Trig
Cyclization of Alkyne-Tethered Cyclohexadienones (ii).
In an oven-dried glass vial, terminal alkyne (0.050 g, 1.0 equiv),
sodium arylsulfinates (0.151 g, 3.0 equiv), diphenyl diselenide
(0.048 g, 0.5 equiv), and K2S2O8 (0.166 g, 2.0 equiv) were
dissolved in 2 mL ACN; the vial was then sealed with a PTFE
septum and purged with argon. The reaction mixture was
stirred continuously for 6 h while being exposed to 5 W blue
LED light at room temperature. Then, the reaction mixture
was diluted with water. It was extracted with ethyl acetate (3 ×
10 mL). Then, to the organic layer was added Na2SO4, and the
mixture was concentrated under reduced pressure. The residue
was directly subjected to flash chromatography on silica gel
(hexane/ethyl acetate) to afford the desired product.
Characterization Data. (4aR,5R,8aR)-8a-Methyl-4-phe-
nyl-5-(phenylselanyl)-3-tosyl-4a,8a-dihydro-2H-chromen-
6(5H)-one (4a). The title compound was prepared according
to the general procedure as described above (i) in an 89% (102
mg) yield; it was purified by column chromatography (20%
EtOAc/hexane; Rf = 0.2) to afford 4a as a white solid (mp:
195−200 °C). 1H NMR (400 MHz, CDCl3): δ 7.41−7.39 (m,
2H), 7.36 (d, J = 8.3 Hz, 2H), 7.29 (dd, J = 12.7, 5.3 Hz, 2H),
7.26−7.23 (m, 2H), 7.21 (dd, J = 7.4, 4.0 Hz, 3H), 7.18−7.14
(m, 3H), 6.54 (d, J = 10.2 Hz, 1H), 6.09 (dd, J = 10.2, 1.3 Hz,
1H), 4.94 (d, J = 17.6 Hz, 1H), 4.66 (dd, J = 17.6, 2.5 Hz, 1H),
3.40 (dd, J = 4.2, 1.2 Hz, 1H), 2.85 (dd, J = 3.9, 2.2 Hz, 1H),
2.40 (s, 3H), 1.46 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
193.6, 146.3, 145.4, 144.2, 138.3, 138.1, 135.5, 134.0, 129.4,
129.1, 128.7, 128.3, 128.0, 127.64, 127.5, 68.4, 61.3, 48.4, 47.4,
22.6, 21.6. IR (neat)νmax: 3608, 1677, 1312, 1146, 751. HRMS
(ESI-TOF): m/z calcd for C 29 H27O 4 SSe [M + H]+ ,
551.07726; found, 551.07898.
(4aR,5R,8aR)-8a-Methyl-5-(phenylselanyl)-4-(p-tolyl)-3-
tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4b). The title
compound was prepared according to the general procedure as
described above (i) in a 90% (100 mg) yield; it was purified by
column chromatography (20% EtOAc/hexane; Rf = 0.2) to
afford 4b as a white solid (mp: 177−182 °C). 1H NMR (400
MHz, CDCl3): δ 7.38 (d, J = 8.0 Hz, 4H), 7.26−7.18 (m, 3H),
7.15 (d, J = 8.1 Hz, 2H), 7.00 (d, J = 7.9 Hz, 2H), 6.90 (s,
2H), 6.51 (d, J = 10.2 Hz, 1H), 6.07 (dd, J = 10.2, 0.8 Hz, 1H),
4.90 (d, J = 17.5 Hz, 1H), 4.62 (dd, J = 17.6, 2.3 Hz, 1H), 3.39
(d, J = 4.0 Hz, 1H), 2.83−2.81 (m, 1H), 2.40 (s, 3H), 2.33 (s,
3H), 1.43 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 193.6,
146.3, 145.7, 144.2, 138.7, 137.9, 134.0, 132.5, 130.3, 129.3,
129.0, 128.6, 128.2, 127.6, 127.4, 68.4, 61.3, 48.5, 47.5, 22.6,
21.6, 21.3. IR (neat)νmax: 3606, 3033, 2975, 1682, 1316, 1152,
1082, 755. HRMS (ESI-TOF): m/z calcd for C30H29O4SSe
[M + H]+, 565.0926; found, 565.0946.
(4aR,5R,8aR)-4-(4-Methoxyphenyl)-8a-methyl-5-(phenyl-
selanyl)-3-tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4c).
The title compound was prepared according to the general
procedure as described above (i) in a 78% (84 mg) yield; it
was purified by column chromatography (20% EtOAc/hexane;
Rf = 0.2) to afford 4c as a white solid (mp: 188−193 °C). 1H
NMR (400 MHz, CDCl3): δ 7.38 (t, J = 7.8 Hz, 4H), 7.25−
7.20 (m, 3H), 7.16 (d, J = 8.1 Hz, 2H), 6.95 (s, 2H), 6.73 (d,
2H), 6.53 (d, J = 10.2 Hz, 1H), 6.08 (dd, J = 10.2, 0.8 Hz, 1H),
4.94 (d, J = 17.6 Hz, 1H), 4.63 (dd, J = 17.6, 2.3 Hz, 1H), 3.81
(s, 3H), 3.37 (d, J = 3.3 Hz, 1H), 2.83 (d, J = 2.1 Hz, 1H),
2.40 (s, 3H), 1.44 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
193.64, 160.0, 146.3, 145.5, 144.1, 138.2, 138.2, 134.0, 130.3,
129.3, 129.1, 128.2, 127.7, 127.4, 113.4, 68.5, 61.4, 55.4, 48.5,
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47.6, 22.6, 21.6. IR (neat)νmax: 3021, 2921, 1681, 1248, 753.
HRMS (ESI-TOF): m/z calcd for C30H29O5SSe [M + H]+,
581.0879; found, 581.0895.
Methyl 4-((4aR,5R,8aR)-8a-methyl-6-oxo-5-(phenylselan-
yl)-3-tosyl-4a,5,6,8a-tetrahydro-2H-chromen-4-yl)benzoate
(4d). The title compound was prepared according to the
general procedure as described above (i) in a 93% (95 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 4d as a white solid (mp:193−198
°C). 1H NMR (500 MHz, CDCl3): δ 7.88 (d, J = 8.0 Hz, 2H),
7.42 (d, J = 8.2 Hz, 2H), 7.38−7.37(m, 2H), 7.28 (d, J = 7.2
Hz, 2H), 7.24 (d, J = 6.9 Hz, 2H), 7.21 (d, J = 8.1 Hz, 3H),
6.54 (d, J = 10.2 Hz, 1H), 6.10 (dd, J = 10.2, 1.0 Hz, 1H), 4.91
(d, J = 17.8 Hz, 1H), 4.65 (dd, J = 17.8, 2.4 Hz, 1H), 3.94 (s,
3H), 3.36 (d, J = 3.3 Hz, 1H), 2.85 (dd, J = 3.5, 2.5 Hz, 1H),
2.43 (s, 3H), 1.47 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
193.4, 166.4, 146.3, 144.8, 144.3, 140.4, 138.9, 137.8, 133.8,
130.3, 130.1, 129.6, 129.2, 128.4, 127.7, 127.5, 68.3, 61.3, 52.3,
48.2, 47.2, 22.6, 21.6. IR (neat)νmax: 3605, 1723, 1684, 1286,
1152, 760. HRMS (ESI-TOF): m/z calcd for C31H29O6SSe
[M + H]+, 609.0825; found, 609.0844.
(4aR,5R,8aR)-8a-Methyl-5-(phenylselanyl)-3-tosyl-4-(3-
(trifluoromethyl)phenyl)-4a,8a-dihydro-2H-chromen-6(5H)-
one (4e). The title compound was prepared according to the
general procedure(i) as described above (i) in an 86% (86 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 4e as a white solid (mp: 203−208
°C). 1H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 7.6 Hz, 2H),
7.40 (dd, J = 18.8, 6.8 Hz, 5H), 7.29 (dt, J = 5.7, 1.9 Hz, 1H),
7.24 (d, J = 7.4 Hz, 2H), 7.23−7.17 (m, 3H), 6.56 (d, J = 10.2
Hz, 1H), 6.11 (dd, J = 10.2, 1.2 Hz, 1H), 4.98 (d, J = 17.9 Hz,
1H), 4.72 (d, J = 17.9 Hz, 1H), 3.33 (d, J = 3.5 Hz, 1H), 2.83−
2.81 (m, 1H), 2.40 (s, 3H), 1.51 (s, 3H). 13C NMR (100
MHz, CDCl3): δ 193.4, 146.2, 144.9, 143.5, 140.0, 137.8,
136.3, 134.0, 129.6, 129.2, 128.5, 127.6, 127.3, 125.6, 125.5,
68.3, 61.3, 48.2, 47.2, 22.7, 21.5. IR (neat)νmax: 3604, 1683,
1329, 1158, 1083, 756. HRMS (ESI-TOF): m/z calcd for
C30H26F3O4SSe [M + H]+, 619.0646; found, 619.0663.
(4aR,5R,8aR)-8a-Methyl-5-(phenylselanyl)-4-(thiophen-2-
yl)-3-tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4f). The
title compound was prepared according to the general
procedure as described above (i) in an 83% (94 mg) yield;
it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 4f as a white solid (mp: 198−203
°C). 1H NMR (400 MHz, CDCl3): δ 7.37−7.31 (m, 4H),
7.24 (dd, J = 5.1, 1.1 Hz, 1H), 7.21−7.16 (m, 2H), 7.15−7.08
(m, 4H), 6.88 (dd, J = 5.0, 3.6 Hz, 1H), 6.46 (d, J = 10.2 Hz,
1H), 6.03 (dd, J = 10.2, 1.2 Hz, 1H), 4.87 (dd, J = 25.8, 13.5
Hz, 1H), 4.64−4.59 (m, 1H), 3.38 (d, J = 5.5 Hz, 1H), 2.19−
2.78 (m, 1H), 2.32 (s, 3H), 1.37 (s, 3H). 13C NMR (100
MHz, CDCl3): δ 193.4, 146.2, 144.3, 141.0, 138.9, 137.6,
135.1, 134.5, 131.4, 130.2, 129.3, 129.1, 128.4, 128.1, 127.7,
127.4, 126.8, 68.6, 61.8, 49.2, 48.2, 22.7, 21.6. IR (neat)νmax:
3615, 1682, 1315, 1152, 1082, 755. HRMS (ESI-TOF): m/z
calcd for C27H25O4S2Se [M + H]+, 557.0334; found, 557.0354.
(4aR,5R,8aR)-4,8a-Dimethyl-5-(phenylselanyl)-3-tosyl-
4a,8a-dihydro-2H-chromen-6(5H)-one (4g). The title com-
pound was prepared according to the general procedure as
described above (i) in an 88% (118 mg) yield; it was purified
by column chromatography (20% EtOAc/hexane; Rf = 0.2) to
afford 4g as a white solid (mp: 184−188 °C). 1H NMR (500
MHz, CDCl3): δ 7.89 (t, J = 6.5 Hz, 2H), 7.36 (d, J = 8.0 Hz,
2H), 7.30−7.26 (m, 1H), 7.22−7.18 (m, 4H), 6.50 (d, J = 10.2
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Hz, 1H), 6.10 (dd, J = 10.2, 1.2 Hz, 1H), 4.64 (dd, J = 17.1,
1.8 Hz, 1H), 4.58−4.54 (m, 1H), 3.61 (dd, J = 4.3, 1.2 Hz,
1H), 2.64 (dd, J = 4.1, 1.7 Hz, 1H), 2.42 (s, 3H), 2.18 (t, J =
2.1 Hz, 3H), 1.38 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
193.77, 147.11, 144.69, 143.73, 138.37, 134.71, 129.89, 129.12,
128.58, 127.51, 127.40, 68.30, 61.50, 48.92, 47.43, 22.76,
21.66, 18.52. IR (neat)νmax: 3019, 2349, 1680, 1214, 1146,
743. HRMS (ESI-TOF): m/z calcd for C24H25O4SSe [M +
H]+, 489.0617; found, 489.0633.
(4aR,5R,8aR)-8a-Isopropyl-4-phenyl-5-(phenylselanyl)-3-
tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4h). The title
compound was prepared according to the general procedure as
described above (i) in 91% (93 mg) yield; it was purified by
column chromatography (20% EtOAc/hexane; Rf = 0.2) to
afford 4h as a white solid (mp: 188−192 °C). 1H NMR (400
MHz, CDCl3): δ 7.41−7.37 (m, 4H), 7.30−7.23 (m, 3H),
7.21−7.15 (m, 5H), 6.89 (s, 2H), 6.63 (d, J = 10.5 Hz, 1H),
6.23 (dd, J = 10.5, 0.9 Hz, 1H), 4.88 (d, J = 17.7 Hz, 1H), 4.65
(dd, J = 17.7, 2.2 Hz, 1H), 3.47 (dd, J = 4.2, 1.2 Hz, 1H), 3.13
(dd, J = 3.9, 1.9 Hz, 1H), 2.40 (s, 3H), 2.33 (dd, J = 13.7, 6.8
Hz, 1H), 1.17 (d, J = 6.7 Hz, 3H), 0.85 (d, J = 6.9 Hz, 3H).
13
C NMR (125 MHz, CDCl3): δ 193.6, 144.9, 144.2, 141.7,
138.2, 138.1, 135.8, 133.8,130.4, 129.3, 129.0, 128.5, 128.2,
128.0, 127.5, 73.1, 61.2, 48.4, 45.0, 29.3, 21.6, 18.5, 15.7. IR
(neat)νmax: 3357, 2925, 1677, 1145, 1022, 748. HRMS (ESI-
TOF): m/z calcd for C31H31O4SSe [M + H]+, 579.1082;
found, 579.1102.
(4aR,5R,8aR)-4,8a-Diphenyl-5-(phenylselanyl)-3-tosyl-
4a,8a-dihydro-2H-chromen-6(5H)-one (4i). The title com-
pound was prepared according to the general procedure as
described above (i) in an 85% (86 mg) yield; It was purified by
column chromatography (20% EtOAc/hexane; Rf = 0.2) to
afford 4i as a white solid (mp: 228−233 °C). 1H NMR (500
MHz, CDCl3): δ 7.49−7.42(m, 8H), 7.33−7.21 (m, 7H), 6.93
(d, J = 8.2 Hz, 2H), 6.86 (d, J = 8.2 Hz, 2H), 6.63 (d, J = 10.2
Hz, 1H), 6.05 (d, J = 10.2 Hz, 1H), 4.94 (t, J = 15.1 Hz, 1H),
4.38−4.34 (m, 1H), 3.81 (s, 1H), 3.62 (d, J = 3.9 Hz, 1H),
2.32 (d, J = 24.0 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ
193.6, 147.1, 145.7, 143.7, 139.0, 138.7, 137.8, 135.3, 134.3,
129.4, 129.1, 129.0, 128.9, 128.8, 128.4, 128.1, 127.1, 126.9,
126.2, 72.9, 62.1, 48.3, 45.0, 21.5. IR (neat)νmax: 3452, 2980,
1680, 1316, 1150, 761. HRMS (ESI-TOF): m/z calcd for
C34H29O4SSe [M + H]+, 613.0929; found, 613.0946.
(4aR,5R,8aR)-7,8a-Dimethyl-4-phenyl-5-(phenylselanyl)-
3-tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4j). The title
compound was prepared according to the general procedure as
described above (i) in an 86% (96 mg) yield; it was purified by
column chromatography (20% EtOAc/hexane; Rf = 0.2) to
afford 4j as a white solid (mp: 118−122 °C). 1H NMR (500
MHz, CDCl3): δ 7.30 (dd, J = 17.0, 7.4 Hz, 4H), 7.23−7.19
(m, 3H), 7.16 (d, J = 7.1 Hz, 2H), 7.15−7.10 (m, 3H), 7.07
(d, J = 7.7 Hz, 2H), 6.23 (s, 1H), 4.86 (d, J = 17.6 Hz, 1H),
4.56 (d, J = 17.5 Hz, 1H), 3.35 (d, J = 3.2 Hz, 1H), 2.79 (s,
1H), 2.33 (s, 3H), 1.80 (s, 3H), 1.37 (s, 3H). 13C NMR (125
MHz, CDCl3): δ 194.1, 145.5, 144.2, 141.6, 138.3, 138.2,
135.7, 134.5, 134.0, 130.4, 129.3, 129.1, 128.7, 128.2,127.5,
68.9, 61.3, 48.6, 47.7, 22.9, 21.6, 16.3. IR (neat) νmax: 3340,
2950, 1676, 1315, 1151, 1097, 752. HRMS (ESI-TOF): m/z
calcd for C30H29O4SSe [M + H]+, 565.0927; found, 565.0946.
(4aR,5R,8aR)-8a-Methyl-4-phenyl-5-(p-tolylselanyl)-3-
tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4k). The title
compound was prepared according to the general procedure as
described above (i) in an 88% (98 mg) yield; it was purified by
https://doi.org/10.1021/acsomega.3c03362
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column chromatography (20% EtOAc/hexane; Rf = 0.2) to
afford 4k as a white solid (mp:175−178 °C). 1H NMR (400
MHz, CDCl3): δ 7.29 (d, J = 8.3 Hz, 2H), 7.21 (dt, J = 6.6, 5.2
Hz, 4H), 7.13 (d, J = 7.5 Hz, 2H), 7.07 (d, J = 8.0 Hz, 3H),
6.96 (d, J = 7.8 Hz, 2H), 6.45 (d, J = 10.2 Hz, 1H), 6.00 (dd, J
= 10.2, 1.3 Hz, 1H), 4.86 (d, J = 17.6 Hz, 1H), 4.57 (dd, J =
17.6, 2.5 Hz, 1H), 3.26 (dd, J = 4.2, 1.2 Hz, 1H), 2.76 (dd, J =
3.9, 2.3 Hz, 1H), 2.32 (s, 3H), 2.23 (s, 3H), 1.38 (s, 3H). 13C
NMR (125 MHz, CDCl3): δ 210.8, 197.8, 193.3, 146.1, 145.4,
144.2, 138.5, 138.2, 138.0, 135.5, 134.5, 129.9, 129.3, 128.7,
127.9, 127.6, 127.4, 68.4, 61.2, 48.3, 47.3, 22.6, 21.6, 21.2. IR
(neat)νmax: 3352, 2944, 2831, 1024, 750. HRMS (ESI-TOF):
m/z calcd for C30H29O4SSe [M + H]+, 565.0926; found,
565.0946.
(4aR,5R,8aR)-5-((4-Methoxyphenyl)selanyl)-8a-methyl-4-
phenyl-3-(phenylsulfonyl)-4a,8a-dihydro-2H-chromen-
6(5H)-one (4l). The title compound was prepared according to
the general procedure as described above (i) in an 85% (93
mg) yield; it was purified by column chromatography (20%
EtOAc/hexane; Rf = 0.2) to afford 4l as a white solid (mp:
180−185 °C). 1H NMR (500 MHz, CDCl3): δ 7.51 (t, J = 7.4
Hz, 1H), 7.47 (d, J = 7.5 Hz, 2H), 7.36−7.28 (m, 6H), 7.22 (t,
J = 7.1 Hz, 3H), 6.76 (d, J = 8.6 Hz, 2H), 6.53 (d, J = 10.2 Hz,
1H), 6.08 (d, J = 10.1 Hz, 1H), 4.97 (d, J = 17.7 Hz, 1H), 4.67
(dd, J = 17.7, 2.1 Hz, 1H), 3.76 (s, 3H), 3.26 (d, J = 3.4 Hz,
1H), 2.83 (s, 1H), 1.45 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 193.2, 160.1, 146.0, 145.9, 141.0, 138.1, 136.7,
135.3, 133.2, 128.7, 128.0, 127.6, 127.3, 120.2, 114.8, 68.4,
61.2, 55.2, 48.3, 48.1, 22.6. IR (neat)νmax: 3458, 2962, 1674,
1584, 1244, 1148, 692. HRMS (ESI-TOF): m/z calcd for
C29H27O5SSe [M + H]+, 567.0723; found, 567.0738.
(4aR,5R,8aR)-5-((3-Fluorophenyl)selanyl)-8a-methyl-4-
phenyl-3-tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4m).
The title compound was prepared according to the general
procedure as described above (i) in a 90% (99 mg) yield; it
was purified by column chromatography (20% EtOAc/hexane;
Rf = 0.2) to afford 4m as a white solid (mp: 222−228 °C). 1H
NMR (400 MHz, CDCl3): δ 7.35 (d, J = 8.3 Hz, 2H), 7.29 (d,
J = 7.5 Hz, 1H), 7.21−7.14 (m, 7H), 7.12−7.09 (m, 1H),
6.98−6.93 (m, 2H), 6.55 (d, J = 10.2 Hz, 1H), 6.09 (dd, J =
10.2, 1.2 Hz, 1H), 4.93 (d, J = 17.7 Hz, 1H), 4.66 (dd, J = 17.7,
2.4 Hz, 1H), 3.41 (dd, J = 4.2, 1.1 Hz, 1H), 2.86 (dd, J = 3.9,
2.3 Hz, 1H), 2.40 (s, 3H), 1.47 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 193.6, 163.5, 161.0, 146.6, 145.2, 144.4, 129.4,
129.1, 129.1, 128.8, 128.0, 127.6, 127.5, 120.4, 120.1, 115.3,
115.1, 68.4, 61.3, 48.3, 47.4, 22.5, 21.6. IR (neat)νmax: 3462,
2968, 1670, 1582, 1240, 1142, 720. HRMS (ESI-TOF): m/z
calcd for C29H26FO4SSe [M + H]+, 569.0681; found,
569.0695.
(4aR,5R,8aR)-5-((2-Fluorophenyl)selanyl)-8a-methyl-4-
phenyl-3-tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4n).
The title compound was prepared according to the general
procedure as described above (i) in an 80% (88 mg) yield; it
was purified by column chromatography (20% EtOAc/hexane;
Rf = 0.2) to afford 4n as a white solid (mp: 178−183 °C). 1H
NMR (500 MHz, CDCl3): δ 7.43−7.40 (m, 1H), 7.37 (d, J =
8.2 Hz, 2H), 7.32−7.27 (m, 2H), 7.23 (t, J = 7.7 Hz, 3H), 7.14
(d, J = 8.1 Hz, 2H), 7.05−7.00 (m, 3H), 6.55 (d, J = 10.2 Hz,
1H), 6.06 (dd, J = 10.2, 1.0 Hz, 1H), 4.92 (d, J = 17.7 Hz, 1H),
4.67 (dd, J = 17.7, 2.4 Hz, 1H), 3.55 (dd, J = 4.0, 0.9 Hz, 1H),
2.86 (dd, J = 3.5, 2.5 Hz, 1H), 2.38 (s, 3H), 1.48 (s, 3H). 13C
NMR (100 MHz, CDCl3): δ. 193.0, 163.3, 160.9, 146.2, 145.2,
144.2, 138.2, 137.8, 136.4, 135.3, 130.7, 130.7, 129.4, 128.6,
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127.9, 127.4, 127.3, 124.8, 124.8, 116.5, 116.2, 115.5, 115.3,
68.5, 61.3, 48.4, 45.6, 22.5, 21.5. IR (neat) νmax: 3022, 2976,
1674, 1443, 1146, 745. HRMS (ESI-TOF): m/z calcd for
C29H26FO4SSe [M + H]+: 569.0681; found, 569.0695.
(4aR,5R,8aR)-5-((4-Methoxyphenyl)selanyl)-8a-methyl-4-
phenyl-3-tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4o).
The title compound was prepared according to the general
procedure as described above (i) in a 95% (107 mg) yield; it
was purified by column chromatography (20% EtOAc/hexane;
Rf = 0.2) to afford 4o as a white solid (mp: 205−209 °C). 1H
NMR (400 MHz, CDCl3): δ 7.37−7.29 (m, J = 15.1, 7.4 Hz,
5H), 7.26−7.23 (m, 3H), 7.14 (d, J = 8.0 Hz, 3H), 6.76 (d, J =
8.6 Hz, 2H), 6.52 (d, J = 10.2 Hz, 1H), 6.07 (d, J = 10.2 Hz,
1H), 4.94 (d, J = 17.6 Hz, 1H), 4.64 (dd, J = 17.6, 2.1 Hz, 1H),
3.76 (s, 3H), 3.27 (d, J = 3.5 Hz, 1H), 2.83 (s, 1H), 2.39 (s,
3H), 1.44 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 193.3,
160.1, 146.1, 145.4, 144.2, 138.2, 138.0, 136.7, 135.5, 129.3,
128.7, 127.9, 127.6, 127.4, 120.3, 114.7, 68.4, 61.2, 55.2, 48.3,
48.2, 22.6, 21.6. IR (neat)νmax: 3420, 2948, 1680, 1495, 1248,
1151, 763. HRMS (ESI-TOF): m/z calcd for C30H29O5SSe
[M + H]+, 581.0885; found, 581.0895.
(4aR,5R,8aR)-8a-Methyl-4-phenyl-5-(thiophen-2-ylselan-
yl)-3-tosyl-4a,8a-dihydro-2H-chromen-6(5H)-one (4p). The
title compound was prepared according to the general
procedure as described above (i) in an 85% (92 mg) yield;
it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 4p as a white solid (mp: 180−185
°C). 1H NMR (400 MHz, CDCl3): δ 7.37 (d, J = 7.5 Hz, 3H),
7.33−7.26 (m, 4H), 7.15 (d, J = 8.0 Hz, 3H), 7.08 (d, J = 2.8
Hz, 1H), 6.94 (dd, J = 5.1, 3.6 Hz, 1H), 6.53 (d, J = 10.2 Hz,
1H), 6.09 (d, J = 10.2 Hz, 1H), 4.92 (d, J = 17.6 Hz, 1H), 4.65
(dd, J = 17.7, 2.2 Hz, 1H), 3.29 (d, J = 3.2 Hz, 1H), 2.80 (s,
1H), 2.39 (s, 3H), 1.46 (s, 3H). 13C NMR (101 MHz,
CDCl3): δ 192.9, 146.1, 145.3, 144.3, 142.4, 138.2, 137.9,
137.12, 135.4, 132.1, 129.4, 128.8, 128.1, 128.0, 127.5, 127.4,
124.1, 68.5, 61.3, 50.4, 48.4, 40.2, 22.3, 21.6. IR (neat)νmax:
3428, 2938, 1677, 1312, 1146, 703. HRMS (ESI-TOF): m/z
calcd for C27H25O4S2Se [M + H]+, 557.0339; found, 557.0354.
(4aR,5R,8aR)-8a-Methyl-4-phenyl-3-(phenylsulfonyl)-5-
(p-tolylselanyl)-4a,8a-dihydro-2H-chromen-6(5H)-one (4q).
The title compound was prepared according to the general
procedure as described above (i) in an 80% (85 mg) yield; it
was purified by column chromatography (20% EtOAc/hexane;
Rf = 0.2) to afford 4q as a white solid (mp:140−145 °C). 1H
NMR (400 MHz, CDCl3): δ 7.46−7.39 (m, 3H), 7.27 (dd, J =
14.6, 6.5 Hz, 3H), 7.24−7.19 (m, 3H), 7.13 (t, J = 7.6 Hz,
2H), 6.97 (d, J = 7.9 Hz, 3H), 6.46 (d, J = 10.2 Hz, 1H), 6.01
(dd, J = 10.2, 1.1 Hz, 1H), 4.89 (d, J = 17.7 Hz, 1H), 4.61 (dd,
J = 17.7, 2.4 Hz, 1H), 3.26 (dd, J = 4.1, 1.0 Hz, 1H), 2.78−
2.76 (m, 1H), 2.23 (s, 3H), 1.39 (s, 3H). 13C NMR (125
MHz, CDCl3): δ 193.3, 146.1, 145.9, 141.0, 138.6, 138.1,
135.3, 134.6, 133.2, 130.0, 128.8, 128.7, 128.0, 127.6, 127.3,
126.3, 68.4, 61.3, 48.3, 47.6, 22.6, 21.2. IR (neat)νmax: 3450,
2980, 1678, 1313, 1151, 1082, 728. HRMS (ESI-TOF): m/z
calcd for C29H27O4SSe [M + H]+, 551.07726; found,
551.07898.
(4aR,5R,8aR)-3-((4-Chlorophenyl)sulfonyl)-8a-methyl-4-
phenyl-5-(phenylselanyl)-4a,8a-dihydro-2H-chromen-6(5H)-
one (4r). The title compound was prepared according to the
general procedure as described above (i) in an 86% (95 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 4r as a white solid (mp:155−160
°C). 1H NMR (500 MHz, CDCl3): δ 7.41−7.39 (m, 2H),
https://doi.org/10.1021/acsomega.3c03362
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7.37−7.34 (m, 2H), 7.32−7.29 (m, 3H), 7.28−7.21 (m, 4H),
7.20 (t, J = 7.9 Hz, 2H), 6.98 (s, 1H), 6.54 (d, J = 10.2 Hz,
1H), 6.10 (dd, J = 10.2, 1.2 Hz, 1H), 4.96 (d, J = 17.7 Hz, 1H),
4.68 (dd, J = 17.7, 2.5 Hz, 1H), 3.39 (dd, J = 4.2, 1.2 Hz, 1H),
2.86 (dd, J = 3.8, 2.4 Hz, 1H), 1.47 (s, 3H). 13C NMR (100
MHz, CDCl3): δ 193.4, 146.2, 139.9, 139.4, 138.1, 135.1,
133.9, 130.1, 129.1, 129.0, 128.8, 128.3, 128.1, 127.7, 68.4,
61.1, 48.4, 47.3, 22.6. IR (neat)νmax: 3020, 2852, 1673, 1313,
1148, 752. HRMS (ESI-TOF): m/z calcd for C28H24O4ClSSe
[M + H]+, 571.0222; found, 571.0246.
(4aR,5R,8aR)-3-(Cyclopropylsulfonyl)-8a-methyl-4-phe-
nyl-5-(phenylselanyl)-4a,8a-dihydro-2H-chromen-6(5H)-one
(4s). The title compound was prepared according to the
general procedure as described above (i) in an 82% (79 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 4s as a white solid (mp: 144−148
°C). 1H NMR (500 MHz, CDCl3): δ 7.50−7.47 (m, 2H),
7.38 (s, 4H), 7.31−7.24 (m, 4H), 6.58 (d, J = 10.2 Hz, 1H),
6.12 (dd, J = 10.2, 1.3 Hz, 1H), 4.83 (d, J = 17.6 Hz, 1H), 4.58
(dd, J = 17.6, 2.5 Hz, 1H), 3.51 (dd, J = 4.3, 1.2 Hz, 1H), 3.03
(dd, J = 3.9, 2.4 Hz, 1H), 2.04 (dq, J = 8.0, 4.9 Hz, 1H), 1.57
(s, 3H), 1.21 (ddt, J = 10.0, 6.8, 4.9 Hz, 1H), 1.12−1.06 (m,
1H), 0.97−0.92 (m, 1H), 0.89−0.84 (m, 1H). 13C NMR (100
MHz, CDCl3): δ 193.5, 146.3, 144.3, 137.8, 136.1, 134.0,
130.1, 129.2, 129.2, 128.4, 128.3, 127.6, 68.4, 61.3, 48.2, 47.1,
32.5, 22.6, 5.8, 5.3. IR (neat)νmax: 3051, 2976, 1672, 1300,
1144, 701. HRMS (ESI-TOF): m/z calcd for C25H25O4SSe
[M + H]+, 501.0621; found, 501.0633.
(4aR,5R,8aR)-4-(2-Fluorophenyl)-8a-methyl-5-(phenylse-
lanyl)-3-(phenylsulfonyl)-4a,8a-dihydro-2H-chromen-6(5H)-
one (4t). The title compound was prepared according to the
general procedure as described above (i) in a 75% (85 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 4t as a white solid (mp: 154−158
ο
C) 1H NMR (400 MHz, CDCl3): δ 7.50−7.42 (m, 4H),
7.38−7.29 (m, 3H), 7.27−7.20 (m, 4H), 7.05−6.96 (m, 3H),
6.79−6.75 (m, 1H), 6.49 (d, J = 10.2 Hz, 1H), 6.00 (dd, J =
10.2, 1.3 Hz, 1H), 4.89 (d, J = 17.9 Hz, 1H), 4.65 (dd, J = 17.9,
2.4 Hz, 1H), 3.52 (dd, J = 4.2, 1.1 Hz, 1H), 2.88 (dd, J = 3.9,
2.3 Hz, 1H), 1.42 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
192.9, 146.3, 140.8, 140.3, 140.0, 136.8, 133.4, 132.1, 131.0,
131.0, 128.9, 127.2, 124.9, 124.8, 123.6, 123.6, 115.6, 115.4,
115.3, 68.7, 61.5, 46.3, 45.8, 22.2.IR (neat)νmax: 3022, 2976,
1674, 1443, 1146, 745. HRMS (ESI-TOF): m/z calcd for
C28H24FO4SSe [M + H]+, 554.0466; found, 554.0476.
(3aS,4R,7aS,Z)-7a-Methyl-4-(phenylselanyl)-3-(tosyl-
methylene)-2,3,3a,7a-tetrahydrobenzofuran-5(4H)-one
(6a). The title compound was prepared according to the
general procedure as described above (ii) in an 88% (140 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 6a as a white solid(155−160 °C).
1
H NMR (400 MHz, CDCl3): δ 7.65 (d, J = 8.0 Hz, 2H), 7.57
(d, J = 7.0 Hz, 2H), 7.39−7.29 (m, 5H), 6.44 (d, J = 10.2 Hz,
1H), 6.07 (d, J = 2.0 Hz, 1H), 5.98 (d, J = 10.4 Hz, 1H), 5.12
(dd, J = 17.4, 1.3 Hz, 1H), 4.56 (d, J = 17.4 Hz, 1H), 3.85 (s,
1H), 3.29 (s, 1H), 2.41 (s, 3H), 1.72 (s, 3H). 13C NMR (100
MHz, CDCl3): δ 191.2, 158.5, 148.5, 144.9, 137.6, 135.3,
130.0, 129.5, 129.3, 128.4, 127.2, 123.7, 78.7, 68.2, 53.8, 45.4,
25.0, 21.6. IR (neat)νmax: 3405, 2940, 1683, 1444, 1303, 1145,
742. HRMS (ESI-TOF): m/z calcd for C23H23O4SSe [M +
H]+, 475.0466, Found 475.0476.
(3aS,4R,7aS,Z)-7a-Methyl-4-(p-tolylselanyl)-3-(tosyl-
methylene)-2,3,3a,7a-tetrahydrobenzofuran-5(4H)-one
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(6b). The title compound was prepared according to the
general procedure as described above (iii) in an 87% (143 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 6b as a white solid (mp: 175−180
°C). 1H NMR (500 MHz, CDCl3): δ 7.64 (d, J = 8.2 Hz, 2H),
7.44 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.13 (d, J =
7.8 Hz, 2H), 6.43 (dd, J = 10.4, 1.7 Hz, 1H), 6.04 (d, J = 2.4
Hz, 1H), 5.97 (dd, J = 10.4, 0.9 Hz, 1H), 5.12 (dd, J = 17.4,
2.2 Hz, 1H), 4.58−4.53 (m, 1H), 3.80 (s, 1H), 3.28 (s, 1H),
2.41 (s, 3H), 2.35 (s, 3H), 1.72 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 191.1, 158.6, 148.4, 144.8, 139.7, 137.6, 135.7,
130.4, 130.0, 128.4, 127.2, 124.4, 123.6, 78.7, 68.2, 53.7, 45.6,
25.0, 21.6, 21.3. IR (neat)νmax:3482, 2926, 1675, 1306, 1148,
809. HRMS (ESI-TOF): m/z calcd for C24H25O4SSe [M +
H]+, 489.0621; found, 489. 0633
(3aS,4R,7aS,Z)-4-((4-Methoxyphenyl)selanyl)-7a-methyl-
3-(tosylmethylene)-2,3,3a,7a-tetrahydrobenzofuran-5(4H)-
one (6c). The title compound was prepared according to the
general procedure as described above (ii) in a 92% (156 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 6c as a white solid (mp:153−156
°C). 1H NMR (500 MHz, CDCl3): δ 7.64 (d, J = 7.9 Hz, 2H),
7.47 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 7.8 Hz, 2H), 6.84 (d, J =
8.3 Hz, 2H), 6.43 (d, J = 10.3 Hz, 1H), 6.03 (s, 1H), 5.97 (d, J
= 10.4 Hz, 1H), 5.12 (d, J = 17.4 Hz, 1H), 4.56 (d, J = 17.4
Hz, 1H), 3.80 (s, 3H), 3.74 (s, 1H), 3.27 (s, 1H), 2.41 (s, 3H),
1.72 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 191.1, 160.8,
158.6, 148.4, 144.9, 137.8, 137.6, 130.0, 128.4, 127.2, 123.5,
118.3, 115.2, 78.7, 68.2, 55.3, 53.6, 46.0, 25.0, 21.6. IR
(neat)νmax: 3498, 2979, 1676, 1491, 1246, 1146, 819. HRMS
(ESI-TOF): m/z calcd for C24H25O5SSe [M + H]+, 505.0569;
found, 505.0582.
(3aS,4R,7aS,Z)-4-((3-Fluorophenyl)selanyl)-7a-methyl-3-
(tosylmethylene)-2,3,3a,7a-tetrahydrobenzofuran-5(4H)-
one (6d). The title compound was prepared according to the
general procedure as described above (ii) in a 78% (118 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 6d as a white solid (mp:133−146
°C). 1H NMR (500 MHz, CDCl3): δ 7.76 (d, J = 8.2 Hz,
0.7H), 7.66 (d, J = 8.3 Hz, 2H), 7.35−7.26 (m, 6H), 7.22−
6.98 (m, 2.2.H), 6.92 (d, J = 1.9 Hz, 0.35H), 6.54 (d, J = 10.2
Hz, 0.35H), 6.45 (dd, J = 10.4, 1.7 Hz, 1H), 6.09 (dd, J = 5.0,
2.4 Hz, 1H), 6.04 (d, J = 10.2 Hz, 0.35H), 5.99 (dd, J = 10.4,
1.1 Hz, 1H), 5.12 (dd, J = 17.4, 2.2 Hz, 1H), 5.00 (dd, J =
17.4, 2.3 Hz, 0.35H), 4.93−4.89 (m, 0.35H), 4.57 (dt, J = 17.4,
2.4 Hz, 1H), 4.03 (d, J = 4.9 Hz, 0.35H), 3.87−3.87 (m, 1H),
3.30−3.30 (m, 1H), 3.14−3.17 (m, 0.35H), 2.43 (s, 1H), 2.42
(s, 3H), 1.70 (s, 3H), 1.39 (s, 1H). 13C NMR (100 MHz,
CDCl3): δ 192.3, 191.0, 163.6, 161.1, 158.2, 156.9, 148.7,
148.0, 144.9, 137.9, 137.5, 130.8, 130.7, 130.6, 130.6, 130.4,
130.3, 130.0, 129.5, 129.4, 128.5, 128.3, 127.2, 127.1, 123.8,
123.7, 122.0, 121.8, 121.5, 121.3, 116.5, 116.3, 116.0, 115.8,
79.5, 78.6, 69.1, 68.2, 53.8, 52.3, 49.7, 45.3, 25.0, 22.7, 21.6 IR
(neat)νmax: 3049, 2929, 1672, 1475, 1280, 1148, 811. HRMS
(ESI-TOF): m/z calcd for C23H22O4FSSe [M + H]+,
493.0367; found, 493.0382.
(3aS,4R,7aS,Z)-7a-Methyl-3-((phenylsulfonyl)methylene)-
4-(p-tolylselanyl)-2,3,3a,7a-tetrahydrobenzofuran-5(4H)-
one (6e). The title compound was prepared according to the
general procedure as described above (ii) in a 91% (145 mg)
yield; it was purified by column chromatography (20% EtOAc/
hexane; Rf = 0.2) to afford 6e as a white solid (mp: 158−163
°C). 1H NMR (400 MHz, CDCl3): δ 7.78−7.76(m, 2H),
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ACS Omega http://pubs.acs.org/journal/acsodf
7.61−7.53 (m, 1H), 7.51−7.44 (m, 2H), 7.26−7.72 (m, 2H),
7.13 (d, J = 7.8 Hz, 2H), 6.43 (dd, J = 10.4, 1.8 Hz, 1H), 6.43
(dd, J = 10.4, 1.8 Hz, 1H), 6.07 (q, J = 2.5 Hz, 1H), 5.97 (dd, J
= 10.4, 1.2 Hz, 1H), 5.13 (dd, J = 17.5, 2.3 Hz, 1H), 4.56 (dt, J
= 17.5, 2.5 Hz, 1H), 3.80 (dd, J = 2.3, 1.3 Hz, 1H), 3.29−3.28
(m, 1H), 2.35 (s, 3H), 1.73 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 191.10, 159.29, 148.38, 140.51, 139.71, 135.68,
133.77, 130.38, 129.35, 128.42, 127.13, 124.39, 123.30, 78.72,
77.00, 68.17, 53.75, 45.60, 24.96, 21.27. IR (neat) νmax: 3492,
2974, 1677, 1305, 1147, 1082, 802. HRMS (ESI-TOF): m/z
calcd for C23H23O4SSe [M + H]+, 475.0466; found, 475.0476.
(3aS,4R,7aS,Z)-4-((4-Methoxyphenyl)selanyl)-7a-methyl-
3-((phenylsulfonyl)methylene)-2,3,3a,7a-tetrahydrobenzo-
furan-5(4H)-one (6f). The title compound was prepared
according to the general procedure as described above (ii) in
an 86% (142 mg) yield; it was purified by column
chromatography (20% EtOAc/hexane; Rf = 0.2) to afford 6f
as a white solid (mp: 160−165 °C). 1H NMR (400 MHz,
CDCl3): δ 7.76 (dd, J = 5.2, 3.3 Hz, 2H), 7.62−7.58 (m, 1H),
7.52−7.45 (m, 4H), 6.86−6.82 (m, 2H), 6.43 (dd, J = 10.4, 1.8
Hz, 1H), 6.06 (q, J = 2.5 Hz, 1H), 5.97 (dd, J = 10.4, 1.2 Hz,
1H), 5.12 (dd, J = 17.5, 2.3 Hz, 1H), 4.56 (dt, J = 17.5, 2.5 Hz,
1H), 3.79 (s, 3H), 3.75 (dd, J = 2.2, 1.3 Hz, 1H), 3.33−3.23
(m, 1H), 1.72 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 191.1,
160.8, 159.3, 148.3, 140.5, 137.7, 133.8, 129.3, 128.4, 127.1,
123.3, 118.2, 115.2, 78.7, 68.2, 55.3, 53.7, 45.9, 25.0. IR
(neat)νmax:3499, 2478, 1678, 1298, 1249, 1150, 755 HRMS
(ESI-TOF): m/z calcd for C23H23O5SSe [M + H]+, 491.0415;
found, 491.0421.
(3aS,4R,7aS,Z)-3-(((4-Chlorophenyl)sulfonyl)methylene)-
7a-methyl-4-(phenylselanyl)-2,3,3a,7a-tetrahydrobenzofur-
an-5(4H)-one (6g). The title compound was prepared
according to the general procedure as described above (ii) in
an 80% (133 mg) yield; it was purified by column
chromatography (20% EtOAc/hexane; Rf = 0.2) to afford 6g
as a white solid (mp: 194−198 °C). 1H NMR (500 MHz,
CDCl3): δ 7.70 (d, J = 8.5 Hz, 2H), 7.57 (d, J = 7.0 Hz, 2H),
7.48 (d, J = 8.4 Hz, 2H), 7.35 (dt, J = 24.7, 7.2 Hz, 3H), 6.44
(dd, J = 10.4, 1.4 Hz, 1H), 6.07 (d, J = 0.9 Hz, 1H), 5.99 (d, J
= 10.4 Hz, 1H), 5.11 (dd, J = 17.6, 1.8 Hz, 1H), 4.55 (dt, J =
17.6, 2.4 Hz, 1H), 3.86 (d, J = 0.7 Hz, 1H), 3.31 (s, 1H), 1.73
(s, 3H). 13C NMR (100 MHz, CDCl3): δ 191.18, 159.90,
148.42, 140.56, 138.93, 135.32, 129.70, 129.55, 129.32, 128.61,
128.45, 128.03, 122.99, 78.74, 77.00, 68.13, 53.92, 45.34,
24.96. IR (neat)νmax;3049, 2929, 1672, 1313, 1148, 1086, 752.
HRMS (ESI-TOF): m/z calcd for C22H20O4ClSSe [M + H]+,
494.9913; found, 494.9930.
(3aS,4R,7aS,Z)-3-((Cyclopropylsulfonyl)methylene)-7a-
methyl-4-(phenylselanyl)-2,3,3a,7a-tetrahydrobenzofuran-
5(4H)-one (6h). The title compound was prepared according
to the general procedure as described above (ii) in a 79% (112
mg) yield; it was purified by column chromatography (20%
EtOAc/hexane; Rf = 0.2) to afford 6h as a white solid (mp:
172−177 °C). 1H NMR (500 MHz, CDCl3): δ 7.64−7.62 (m,
2H), 7.42−7.36 (m, 3H), 6.46 (dd, J = 10.4, 1.8 Hz, 1H), 6.09
(q, J = 2.6 Hz, 1H), 6.04 (dd, J = 10.4, 1.3 Hz, 1H), 5.02 (dd, J
= 17.4, 2.3 Hz, 1H), 4.48 (dt, J = 17.4, 2.5 Hz, 1H), 3.95 (dd, J
= 2.3, 1.3 Hz, 1H), 3.35 (dt, J = 4.2, 2.0 Hz, 1H), 2.30 (tt, J =
8.0, 4.8 Hz, 1H), 1.75 (s, 3H), 1.22−1.10 (m, 2H), 1.04−0.93
(m, 2H). 13C NMR (100 MHz, CDCl3): δ 191.4, 159.3, 148.6,
135.3, 129.6, 129.3, 128.4, 128.2, 121.6, 78.6, 68.1, 53.8, 45.6,
31.6, 25.0, 5.2, 4.9. IR (neat)νmax: 3047, 2930, 1671, 1285,
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1131, 1048, 746. HRMS (ESI-TOF): m/z calcd for
C19H21O4SSe [M + H]+, 425.0305; found, 425.0320.
(3aS,4R,7aS,Z)-7a-Methyl-4-(phenylselanyl)-3-
((phenylsulfonyl)methylene)-2,3,3a,7a-tetrahydrobenzofur-
an-5(4H)-one (6i). The title compound was prepared
according to the general procedure as described above (ii) in
a 93% (144 mg) yield; it was purified by column
chromatography (20% EtOAc/hexane; Rf = 0.2) to afford 6i
as a white solid (mp: 162−168 °C). 1H NMR (400 MHz,
CDCl3): δ 7.79−7.71 (m, 2H), 7.61−7.51 (m, 6H), 7.36−7.3
(m, 2H), 6.44 (dd, J = 10.4, 1.8 Hz, 1H), 6.09 (q, J = 2.5 Hz,
1H), 5.98 (dd, J = 10.4, 1.2 Hz, 1H), 5.13 (dd, J = 17.5, 2.3
Hz, 1H), 4.57 (dt, J = 17.5, 2.5 Hz, 1H), 3.86 (dd, J = 2.3, 1.3
Hz, 1H), 3.32−3.31 (m, 1H), 1.73 (s, 3H). 13C NMR (100
MHz, CDCl3): δ 191.2, 159.2, 148.5, 135.3, 133.8, 129.6,
129.4, 129.3, 128.5, 127.2, 123.4, 78.7, 68.2, 53.9, 45.4, 25.0.
IR (neat)νmax: 3492, 2974, 1677, 1305, 1147, 1082, 802.
HRMS (ESI-TOF): m/z calcd for C22H21O4SSe [M + H]+,
461.0302; found, 461.0320.
(3aS,4R,7aS,Z)-6,7a-Dimethyl-4-(phenylselanyl)-3-(tosyl-
methylene)-2,3,3a,7a-tetrahydrobenzofuran-5(4H)-one (6j).
The title compound was prepared according to the general
procedure as described above (ii) in an 85% (127 mg) yield; it
was purified by column chromatography (20% EtOAc/hexane;
Rf = 0.2) to afford 6j as a white solid (mp:143−146 °C). 1H
NMR (400 MHz, CDCl3): δ 7.57 (d, J = 8.0 Hz, 2H), 7.48 (d,
J = 6.9 Hz, 2H), 7.31−7.18 (m, 5H), 6.12 (s, = 1H), 5.99 (d, J
= 1.9 Hz, 1H), 5.00 (d, J = 17.4 Hz, 1H), 4.44 (d, J = 17.4 Hz,
1H), 3.80 (d, J = 1.9 Hz, 1H), 3.20 (s, 1H), 2.34 (s, 3H), 1.69
(s, 3H), 1.62 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 191.8,
159.2, 144.8, 143.6, 137.7, 135.2, 129.9, 129.5, 129.1, 127.1,
123.5, 79.1, 68.0, 54.1, 45.8, 25.4, 21.6, 16.3. IR (neat)νmax:
3478, 2977, 1672, 1302, 1145, 1047, 741. HRMS (ESI-TOF):
m/z calcd for C24H25O4SSe [M + H]+, 489.0621; found,
457.0633.
(3aS,4R,7aS,Z)-4-((2-Fluorophenyl)selanyl)-7a-methyl-3-
((phenylsulfonyl)methylene)-2,3,3a,7a-tetrahydrobenzofur-
an-5(4H)-one (6k). The title compound was prepared
according to the general procedure as described above (ii) in
a 78% (125 mg) yield; it was purified by column
chromatography (20% EtOAc/hexane; Rf = 0.2) to afford 6k
as a white solid (mp:133−136 οC). 1H NMR (400 MHz,
CDCl3)δ 7.73−7.71 (m, 2H), 7.55−7.53 (m, 1H), 7.50−7.43
(m, 3H), 7.32 (tdd, J = 7.2, 5.3, 1.7 Hz, 1H), 7.08−7.02 (m,
2H), 6.39 (dd, J = 10.4, 1.8 Hz, 1H), 6.05 (q, J = 2.5 Hz, 1H),
5.90 (dd, J = 10.4, 1.3 Hz, 1H), 5.06 (dd, J = 17.5, 2.3 Hz,
1H), 4.50 (dt, J = 17.4, 2.5 Hz, 1H), 3.93 (dd, J = 2.2, 1.3 Hz,
1H), 3.24−3.22 (m, 1H), 1.67 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 190.62, 159.12, 148.57, 140.48, 137.26, 133.81,
131.93, 131.85, 129.38, 128.29, 127.13, 125.15, 123.48, 116.08,
115.85, 114.64, 114.42, 78.59, 68.21, 53.45, 43.70, 24.92. IR
(neat)νmax: 3049, 2929, 1672, 1475, 1280, 1148, 811. HRMS
(ESI-TOF):m/z calcd for C22H20FO4SSe [M + H]+, 478.0153;
found, 478.0158.
8a-Methyl-4-phenyl-3-tosyl-2H-chromen-6(8aH)-one (7).
The title compound was prepared according to the general
procedure as described above in a 75% (25 mg) yield; it was
purified by column chromatography (30% EtOAc/hexane; Rf =
0.2) to afford 7 as a colorless sticky solid. 1H NMR (500 MHz,
CDCl3): δ 7.24 (ddd, J = 7.6, 2.5, 1.2 Hz, 1H), 7.13 (t, J = 7.9
Hz, 4H), 7.03−7.01 (m, 2H), 6.99 (s, 1H), 6.88 (d, J = 7.2 Hz,
2H), 6.48 (s, 1H), 6.26 (d, J = 10.0 Hz, 1H), 4.93 (d, J = 18.9
Hz, 1H), 4.79 (d, J = 18.9 Hz, 1H), 2.31 (s, 3H), 1.50 (s, 3H).
https://doi.org/10.1021/acsomega.3c03362
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13
C NMR (100 MHz, CDCl3): δ 181.2, 153.8, 144.5, 144.2,
142.3, 138.1, 134.7, 133.8, 129.4, 128.0, 127.4, 123.9, 70.6,
62.0, 23.8, 21.6. IR (neat)νmax: 1655,1485,1070,958,751.
HRMS (ESI-TOF): m/z calcd for C23 H19 O 4 S =
391.10112[M + H]+, 391.0998; found, 391.0998.
7a-Methyl-3-((phenylsulfonyl)methylene)-2,3-dihydro-
benzofuran-5(7aH)-one (8). The title compound was
prepared according to the general procedure as described
above in an 80% (26 mg) yield; it was purified by column
chromatography (EtOAc/hexane) to afford 8 as a colorless
sticky solid. 1H NMR (400 MHz, CDCl3): δ 7.95−7.92 (m,
2H), 7.72−7.68 (m, 1H), 7.62−7.59 (m, 2H), 7.18 (d, J = 9.9
Hz, 1H), 6.72 (t, J = 2.7 Hz, 1H), 6.27 (d, J = 1.4 Hz, 1H),
6.19−6.16 (m, 1H), 5.26 (dd, J = 17.4, 2.6 Hz, 1H), 5.11 (dd, J
= 17.4, 2.7 Hz, 1H), 1.40 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 185., 159.4, 148.1, 147.9, 140.1, 134.3, 129.7,
128.0, 127.6, 123.6, 120.1, 78.7, 68.7, 25.6. IR (neat)νmax:
1669,1303,1076,672 HRMS (ESI-TOF):m/z calcd for
C16H15O4S [M − H]+, 303.0696; found, 303.06856.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.3c03362.
Copies of 1H and 13
C NMR spectra for all new
compounds (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Praveen Reddy Adiyala − Department of Organic Synthesis
and Process Chemistry, CSIR-Indian Institute of Chemical
Technology, Hyderabad 500007 Telangana, India; Academy
of Scientific and Innovative Research (AcSIR), Ghaziabad
201002, India; orcid.org/0000-0003-1587-8265;
Email: praveenreddy@iict.res.in
Authors
Vadla Shiva Prasad − Department of Organic Synthesis and
Process Chemistry, CSIR-Indian Institute of Chemical
Technology, Hyderabad 500007 Telangana, India; Academy
of Scientific and Innovative Research (AcSIR), Ghaziabad
201002, India
Vadithya Ranga Rao − Department of Organic Synthesis and
Process Chemistry, CSIR-Indian Institute of Chemical
Technology, Hyderabad 500007 Telangana, India; Academy
of Scientific and Innovative Research (AcSIR), Ghaziabad
201002, India
Maram Gangadhar − Department of Organic Synthesis and
Process Chemistry, CSIR-Indian Institute of Chemical
Technology, Hyderabad 500007 Telangana, India; Academy
of Scientific and Innovative Research (AcSIR), Ghaziabad
201002, India
Sunil Kumar Nechipadappu − Laboratory of X-Ray
Crystallography, Department of Analytical Chemistry, CSIR-
Indian Institute of Chemical Technology (CSIR-IICT),
Hyderabad 500 007, India; Academy of Scientific and
Innovative Research (AcSIR), Ghaziabad 201002, India;
orcid.org/0000-0002-0042-743X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.3c03362
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Article
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
V.S. thanks DST-Inspire, V.R. thanks CSIR, and M.G. thanks
UGC, for their fellowship. We thank CSIR for financial support
(ref. no. 34/1/TD CLP/NCP FBR 2020 RPPBDD TMD−Se
MI). The authors thank the Director of CSIR-IICT for the
generous support (IICT/Pubs./2023/102).
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