Enantioselective Sulfonation of Enones with Sulfinates by Thiourea/Tertiary-Amine Catalysis

Si-fan Wang; Ming Yan; Jin-yi Shi; Guang-xun Li; Jin-zhong Zhao

doi:10.1055/a-2202-0842

Synlett, Table of Contents

Synlett 2024; 35(12): 1441-1445
DOI: 10.1055/a-2202-0842

letter

Enantioselective Sulfonation of Enones with Sulfinates by Thiourea/Tertiary-Amine Catalysis

Si-fan Wang

^aDepartment of Basic Sciences, Shanxi Agricultural University, Taigu, Shanxi, 030800, P. R. of China

^bNatural Product Research Center, Chengdu Institute of Biology, Chinese Academy of Science, Chengdu, Sichuan 610041, P. R. of China

,

Ming Yan

^aDepartment of Basic Sciences, Shanxi Agricultural University, Taigu, Shanxi, 030800, P. R. of China

^bNatural Product Research Center, Chengdu Institute of Biology, Chinese Academy of Science, Chengdu, Sichuan 610041, P. R. of China

,

Jin-yi Shi

^aDepartment of Basic Sciences, Shanxi Agricultural University, Taigu, Shanxi, 030800, P. R. of China

^bNatural Product Research Center, Chengdu Institute of Biology, Chinese Academy of Science, Chengdu, Sichuan 610041, P. R. of China

,

Guang-xun Li ∗

^bNatural Product Research Center, Chengdu Institute of Biology, Chinese Academy of Science, Chengdu, Sichuan 610041, P. R. of China

,

Jin-zhong Zhao∗

^aDepartment of Basic Sciences, Shanxi Agricultural University, Taigu, Shanxi, 030800, P. R. of China

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Abstract

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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

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References

References and Notes

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15 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 H₃BO₃ (0.3 mmol, 3 equiv) was added. DCE (1 mL) and CHCl₃ (1 mL) were mixed well and added to the flask. H₂O (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). ¹H 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). ¹³C 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 C₂₁H₁₈NaO₃S: 373.0869; found: 373.08716.

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