The first example of regiospecific magnesium carbenoid 1,3-CH insertion: its mechanism and stereochemistry

Shingo Ogata; Shigeyuki Masaoka; Ken Sakai; Tsuyoshi Satoh

doi:10.1016/j.tetlet.2007.05.101

The first example of regiospecific magnesium carbenoid 1,3-CH insertion: its mechanism and stereochemistry

Shingo Ogata
, Shigeyuki Masaoka
, Ken Sakai
, Tsuyoshi Satoh

Inorganic and Analytical Chemistry

Research output: Contribution to journal › Article › peer-review

23 Citations (Scopus)

Abstract

Addition reaction of two geometrical isomers of 1-chlorovinyl p-tolyl sulfoxides, derived from unsymmetrical ketones and chloromethyl p-tolyl sulfoxide, with lithium enolate of tert-butyl acetate gave single isomers of the adduct, respectively. Treatment of each diastereomer with i-PrMgCl resulted in the formation of magnesium carbenoids. Highly regiospecific 1,3-CH insertion reaction was found to take place from the magnesium carbenoids to afford cyclopropanes in high yields. Stereochemistry of the adducts, reaction mechanism, and origin of the regiospecificity are discussed.

Original language	English
Pages (from-to)	5017-5021
Number of pages	5
Journal	Tetrahedron Letters
Volume	48
Issue number	29
DOIs	https://doi.org/10.1016/j.tetlet.2007.05.101
Publication status	Published - Jul 16 2007

All Science Journal Classification (ASJC) codes

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2007.05.101

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title = "The first example of regiospecific magnesium carbenoid 1,3-CH insertion: its mechanism and stereochemistry",

abstract = "Addition reaction of two geometrical isomers of 1-chlorovinyl p-tolyl sulfoxides, derived from unsymmetrical ketones and chloromethyl p-tolyl sulfoxide, with lithium enolate of tert-butyl acetate gave single isomers of the adduct, respectively. Treatment of each diastereomer with i-PrMgCl resulted in the formation of magnesium carbenoids. Highly regiospecific 1,3-CH insertion reaction was found to take place from the magnesium carbenoids to afford cyclopropanes in high yields. Stereochemistry of the adducts, reaction mechanism, and origin of the regiospecificity are discussed.",

keywords = "CH insertion, Cyclopropane, Magnesium carbenoid, Regiospecific reaction, Sulfoxide-magnesium exchange reaction",

author = "Shingo Ogata and Shigeyuki Masaoka and Ken Sakai and Tsuyoshi Satoh",

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T1 - The first example of regiospecific magnesium carbenoid 1,3-CH insertion

T2 - its mechanism and stereochemistry

AU - Ogata, Shingo

AU - Masaoka, Shigeyuki

AU - Sakai, Ken

AU - Satoh, Tsuyoshi

PY - 2007/7/16

Y1 - 2007/7/16

N2 - Addition reaction of two geometrical isomers of 1-chlorovinyl p-tolyl sulfoxides, derived from unsymmetrical ketones and chloromethyl p-tolyl sulfoxide, with lithium enolate of tert-butyl acetate gave single isomers of the adduct, respectively. Treatment of each diastereomer with i-PrMgCl resulted in the formation of magnesium carbenoids. Highly regiospecific 1,3-CH insertion reaction was found to take place from the magnesium carbenoids to afford cyclopropanes in high yields. Stereochemistry of the adducts, reaction mechanism, and origin of the regiospecificity are discussed.

AB - Addition reaction of two geometrical isomers of 1-chlorovinyl p-tolyl sulfoxides, derived from unsymmetrical ketones and chloromethyl p-tolyl sulfoxide, with lithium enolate of tert-butyl acetate gave single isomers of the adduct, respectively. Treatment of each diastereomer with i-PrMgCl resulted in the formation of magnesium carbenoids. Highly regiospecific 1,3-CH insertion reaction was found to take place from the magnesium carbenoids to afford cyclopropanes in high yields. Stereochemistry of the adducts, reaction mechanism, and origin of the regiospecificity are discussed.

KW - CH insertion

KW - Cyclopropane

KW - Magnesium carbenoid

KW - Regiospecific reaction

KW - Sulfoxide-magnesium exchange reaction

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U2 - 10.1016/j.tetlet.2007.05.101

DO - 10.1016/j.tetlet.2007.05.101

M3 - Article

AN - SCOPUS:34250315397

SN - 0040-4039

VL - 48

SP - 5017

EP - 5021

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 29

ER -

The first example of regiospecific magnesium carbenoid 1,3-CH insertion: its mechanism and stereochemistry

Abstract

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