Synthesis 2017; 49(23): 5105-5119
DOI: 10.1055/s-0036-1590894
short review
© Georg Thieme Verlag Stuttgart · New York

Recent Advances in Magnesium Carbenoid Chemistry

Tsutomu Kimura*
  • Department of Chemistry, Graduate School of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan   Email: kimtwo@rs.tus.ac.jp
Further Information

Publication History

Received: 24 June 2017

Accepted after revision: 01 August 2017

Publication Date:
12 September 2017 (eFirst)

Abstract

Magnesium carbenoids are a class of organomagnesium species possessing a halo group at the α-position. The reactions of magnesium carbenoids can be classified into the following three categories: nucleophilic reactions resembling Grignard reagents, electrophilic reactions resembling organic halides, and rearrangements resembling carbenes. This short review summarizes recent studies on magnesium carbenoids reported between 2010 and 2016, and milestone studies reported before 2010 according to the classification of the reactions into the aforementioned three categories.

1 Introduction

2 Structures of Magnesium Carbenoids

3 Reactions of Magnesium Carbenoids as Nucleophiles

3.1 Nucleophilic Reactions of Magnesium Carbenoids

3.2 Nucleophilic Reactions of Magnesium Alkylidene Carbenoids

3.3 Nucleophilic Reactions of Cyclopropylmagnesium Carbenoids

4 Electrophilic Reactions of Magnesium Carbenoids

4.1 Reactions with Nucleophiles Followed by Electrophiles

4.2 Reactions with Nucleophiles Possessing Electrophilic Functional Groups

4.3 Nucleophilic Substitution Followed by β-Elimination

5 Rearrangements of Magnesium Carbenoids

5.1 1,2-Shifts of Magnesium Carbenoids

5.2 1,3-C–H Insertions of Magnesium Carbenoids

5.3 1,5-C–H Insertions of Magnesium Carbenoids

5.4 [2+1] Cycloaddition of a Magnesium Carbenoid

6 Conclusion and Outlook

 
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