Synlett 2024; 35(12): 1441-1445
Enantioselective Sulfonation of Enones with Sulfinates by Thiourea/Tertiary-Amine Catalysis
Si-fan Wang
a
Department of Basic Sciences, Shanxi Agricultural University, Taigu, Shanxi, 030800, P. R. of China
b
Natural Product Research Center, Chengdu Institute of Biology, Chinese Academy of Science, Chengdu, Sichuan 610041, P. R. of China
,
Ming Yan
a
Department of Basic Sciences, Shanxi Agricultural University, Taigu, Shanxi, 030800, P. R. of China
b
Natural Product Research Center, Chengdu Institute of Biology, Chinese Academy of Science, Chengdu, Sichuan 610041, P. R. of China
,
Jin-yi Shi
a
Department of Basic Sciences, Shanxi Agricultural University, Taigu, Shanxi, 030800, P. R. of China
b
Natural Product Research Center, Chengdu Institute of Biology, Chinese Academy of Science, Chengdu, Sichuan 610041, P. R. of China
,
b
Natural Product Research Center, Chengdu Institute of Biology, Chinese Academy of Science, Chengdu, Sichuan 610041, P. R. of China
,
Jin-zhong Zhao∗
a
Department of Basic Sciences, Shanxi Agricultural University, Taigu, Shanxi, 030800, P. R. of China
› Author Affiliations The West Light Foundation of the Chinese Academy of Sciences (25E0C30), and the Sichuan Science and Technology Program (2021ZYD0061).
Abstract
Chiral γ-keto sulfones are significant structures in both organic synthesis and pharmaceutical chemistry. Although there are many choices for obtaining racemic forms, only a few enantioselective methods have been reported. We have developed a simple way for obtaining chiral γ-keto sulfones in moderate yields and moderate enantiomeric ratios. Readily available sulfinates were directly used as substrates that could be converted into sulfinic acids by treatment with boric acid. The bifunctional catalyst forms a chiral ion pair with the sulfinic acid and controls the enantioselectivity of the sulfonation through hydrogen bonding.
Key words
keto sulfones -
organocatalysis -
thioureas -
tertiary amines -
sulfonation
Supporting Information
Supporting information for this article is available online at https://doi.org/10.1055/a-2202-0842.
Supporting Information
Publication History
Received: 24 August 2023
© 2023. Thieme. All rights reserved
Georg Thieme Verlag KG
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Enantioselective Catalytic Reaction; General Procedure
A 50 mL glass flask was charged with the appropriate arenesulfinate 1 (0.1 mmol) and chalcone 2 (0.1 mmol), and then H3 BO3 (0.3 mmol, 3 equiv) was added. DCE (1 mL) and CHCl3 (1 mL) were mixed well and added to the flask. H2 O (20 μL) was added, and the flask was placed in a low-temperature isothermal stirring reactor at 5 ℃ for 48 h. The mixture was filtered and concentrated, and the residue was purified by chromatography [silica gel, PE–DCM (1:5)].
(3R )-1,3-Diphenyl-3-(phenylsulfonyl)propan-1-one (3a)
White solid; yield: 65%. [α]D
28 = –19.5 (c = 0.1, EtOAc); HPLC [Chiralcel IC, hexane/i -PrOH (90:10), 1.0 mL/min, λ = 254 nm]: t
R = 47.028 min (major); t
R = 50.073 min (minor).
1 H NMR (400 MHz, CDCl3 ): δ = 7.96 (d, J = 7.7 Hz, 2 H), 7.58 (q, J = 4.9 Hz, 4 H), 7.48 (t, J = 7.7 Hz, 2 H), 7.40 (t, J = 7.8 Hz, 2 H), 7.22 (d, J = 4.3 Hz, 5 H), 4.97 (dd, J = 9.8, 3.5 Hz, 1 H), 4.16 (dd, J = 17.9, 3.6 Hz, 1 H), 3.97 (dd, J = 17.9, 9.7 Hz, 1 H). 13 C NMR (101 MHz, CDCl3 ): δ = 194.9, 136.9, 136.1, 133.7, 133.7, 132.5, 129.8, 129.0, 128.8, 128.8, 128.8, 128.5, 128.2, 66.5, 36.9. HRMS (ESI): m/z : [M + Na]+ calcd for C21 H18 NaO3 S: 373.0869; found: 373.08716.
