Recent Advances in Magnesium Carbenoid Chemistry

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

Key words

magnesium - carbenoids - carbenes - Grignard reaction - organometallic reagents - rearrangement - sulfoxides

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