Organocatalytic Asymmetric X–H Insertion Reactions of α-Carbonyl Sulfonium Ylides, Sulfoxonium Ylides, and Sulfonium Salts

Ruifeng Hu; Chun-Bao Miao; Wengang Guo; Jianwei Sun

doi:10.1055/a-2550-1635

Synlett, Table of Contents

Synlett 2025; 36(10): 1338-1345
DOI: 10.1055/a-2550-1635

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Organocatalytic Asymmetric X–H Insertion Reactions of α-Carbonyl Sulfonium Ylides, Sulfoxonium Ylides, and Sulfonium Salts

Authors

Ruifeng Hu

^aSchool of Petrochemical Engineering, Changzhou University, Changzhou 213164, P. R. of China
Chun-Bao Miao ∗

^aSchool of Petrochemical Engineering, Changzhou University, Changzhou 213164, P. R. of China
Wengang Guo ∗

^aSchool of Petrochemical Engineering, Changzhou University, Changzhou 213164, P. R. of China
Jianwei Sun ∗

^aSchool of Petrochemical Engineering, Changzhou University, Changzhou 213164, P. R. of China

^bDepartment of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong SAR, P. R. of China

Abstract

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Abstract

Since their initial discovery by Ingold and Jessop in 1930, sulfur ylides have been recognized as a highly versatile class of compounds in organic synthesis. Their reactivity, which closely resembles that of diazo compounds, has enabled them to serve as valuable surrogates for safe and stable carbene precursors, offering unique advantages in large-scale syntheses. However, compared to diazo compounds, the catalytic asymmetric reactions involving sulfur ylides, whether as substrates or intermediates, remain relatively underexplored. In this account, we mainly summarize our recent advancements in this area, focusing particularly on their applications in organocatalytic asymmetric X–H (X = N, N₃, Cl, and C) insertion reactions. These reactions typically involve enantio-determining and rate-determining C–X bond formation in combination with dynamic kinetic resolution, thus leading to both high chemical efficiency and enantiocontrol.

1 Introduction

2 S–H Insertion Reactions of Sulfoxonium Ylides

3 N–H Insertion Reactions of Sulfonium Ylides

4 N–H Insertion Reactions of Sulfoxonium Ylides

5 One-Pot Sequential Ylide Formation and N–H insertion Reactions

6 N₃–H Insertion Reactions of Sulfoxonium Ylides

7 Chlorination of Sulfonium Salts

8 C–H Insertion Reactions of Sulfoxonium Ylides

9 Conclusion and Outlook

Key words

organocatalysis - enantioselectivity - α-carbonyl - sulfonium ylide - sulfoxonium ylide - sulfonium salt - N–H insertion

Full Text

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