Synthesis 2014; 46(07): 842-863
DOI: 10.1055/s-0033-1340856
review
© Georg Thieme Verlag Stuttgart · New York

Recent Advances in the Synthetic Application of Difluorocarbene

Chuanfa Ni
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, P. R. of China   Fax: +86(21)64166128   Email: jinbohu@sioc.ac.cn
,
Jinbo Hu*
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, P. R. of China   Fax: +86(21)64166128   Email: jinbohu@sioc.ac.cn
› Author Affiliations
Further Information

Publication History

Received: 16 December 2013

Accepted after revision: 03 February 2014

Publication Date:
19 February 2014 (online)

Abstract

Difluorocarbene is a versatile, reactive intermediate for use in organic synthesis. Over the past decade, significant progress has been made in difluorocarbene chemistry owing to the increasing demand for various fluorinated molecules. Not only the substrate scope for some classical difluorocarbene reagents has been largely expanded, but also new and environmentally friendly difluorocarbene reagents for difluoromethylation and gem-difluorocyclization have been developed. This review summarizes the difluoromethylation, gem-difluorocyclopropanation, gem-difluorocyclopropenation, gem-difluoroolefination, and trifluoromethylation achieved in the last decade using both the classical and the new difluorocarbene sources.

1 Introduction

2 Difluorocarbene Sources

3 Difluoromethylation

3.1 O-Difluoromethylation

3.2 S-Difluoromethylation

3.3 N-Difluoromethylation

3.4 Difluoromethylation of Ambident N,O- and N,S-Nucleophiles

3.5 Se- and P-Difluoromethylation

3.6 C-Difluoromethylation

3.7 Sn-Difluoromethylation

4 gem-Difluorocyclization

4.1 gem-Difluorocyclopropanation

4.2 gem-Difluorocyclopropenation

5 gem-Difluoroolefination and Related Reactions

6 Trifluoromethylation

7 Miscellaneous

8 Conclusions

 
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