N-Alkylsulfonamides as Useful Carbon Electrophiles

Yonghong Gu; Shi-Kai Tian

doi:10.1055/s-0033-1338460

Synlett, Table of Contents

Synlett 2013; 24(10): 1170-1185
DOI: 10.1055/s-0033-1338460

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N-Alkylsulfonamides as Useful Carbon Electrophiles

Yonghong Gu

^aDepartment of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. of China Fax: +86(551)63601592 Email: tiansk@ustc.edu.cn

,

Shi-Kai Tian*

^aDepartment of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. of China Fax: +86(551)63601592 Email: tiansk@ustc.edu.cn

^bKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China

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Abstract

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Abstract

The cleavage of the sp³ carbon–nitrogen bonds in N-alkylsulfonamides has been utilized for the selective formation of various carbon–carbon and carbon–heteroatom bonds. When N-alkylsulfonamides undergo sp³ carbon–nitrogen bond cleavage in the presence of acid catalysts, the resulting carbocations can react with a broad range of carbon, sulfur, nitrogen, oxygen, or hydride nucleophiles. On the other hand, basic conditions allow N-alkylsulfonamides to act as sp³ carbon electrophiles in reactions with strong nucleophiles. In general, N-benzylic, N-allylic, and N-propargylic sulfonamides serve as suitable substrates, and their reactions with nucleophiles provide ready access to a wide range of functionalized molecules.

1 Introduction

2 Mechanism

3 Reactions with Carbon Nucleophiles

3.1 Active Methylene Compounds

3.2 Ketones and Aldehydes

3.3 Aromatic Compounds

3.4 Alkynes, Alkenes, and Arylallenes

3.5 Silylated Carbon Nucleophiles

3.6 Grignard Reagents

4 Reactions with Sulfur Nucleophiles

4.1 Thiols and Thiophenols

4.2 Thioacetic acid

4.3 Sulfinic Acids

5 Reactions with Nitrogen Nucleophiles

6 Reactions with Oxygen Nucleophiles

7 Reduction

8 Conclusion

Key words

sulfonamides - electrophiles - nucleophiles - carbocations - alkylation - heterocycles

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References

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