A versatile synthesis, including asymmetric synthesis, of bicyclo[n.1.0]alkanes from cyclic ketones via the magnesium carbenoid 1,3-CH insertion as a key reaction

Satoh, Tsuyoshi; Ogata, Shingo; Wakasugi, Daisuke

doi:10.1016/j.tetlet.2006.07.140

Cited by 38 publications

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“…A very interesting synthesis of bicyclo[n.1.0]alkanes from cyclic ketones via the magnesium carbenoid 1,3-CH insertion as a key reaction was reported (Scheme 4). 14 For example, 1-chlorovinyl p-tolyl sulfoxide 24 was synthesized from cyclopentadecanone and chloromethyl p-tolyl sulfoxide in three steps in high overall yield. Lithium enolate of tert-butyl acetate was added to 24 to give an adduct 25 in quantitative yield.…”

Section: Introductionmentioning

confidence: 99%

Recent advances in the chemistry of magnesium carbenoids

Satoh

2007

Chem. Soc. Rev.

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102

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This tutorial review deals with recent advances in the chemistry and synthetic use of magnesium carbenoids. The reactivity of traditional carbenoids (alpha-haloalkyllithium species) was successfully reduced by using magnesium as the metal instead of lithium. Properties of these relatively stable carbenoids, magnesium carbenoids, were widely investigated and it was found that the magnesium carbenoids have very interesting reactivity toward several nucleophiles. The magnesium carbenoids, magnesium cyclopropylidenes, magnesium alkylidene carbenoids, and magnesium beta-oxido carbenoids are generated from alpha-chloroalkyl (or alpha-chloroalkenyl) aryl sulfoxides with a Grignard reagent at low temperature by sulfoxide-magnesium exchange reaction. The stability of the generated magnesium carbenoids and several new reactions based on the electrophilicity of the magnesium carbenoids, including 1,3-CH insertion, are reviewed. Magnesium carbenoids open up the new world of the chemistry of carbenoids.

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Section: Introductionmentioning

confidence: 99%

Recent advances in the chemistry of magnesium carbenoids

Satoh

2007

Chem. Soc. Rev.

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102

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“…Also hydroboration of cyclopropenes with rhodium catalyst and chiral BINAP ligands is effective: Generation of enantiopure 2,2-disubstituted cyclopropyl boronates was achieved in almost quantitative yield (Scheme 35) (131). A ring-closing reaction has also been shown to form cyclopropane in good yield (Scheme 36) (132). Treatment of the sulfoxide with iPrMgCl led to formation of the bicycle[4.1.0]hept-2-ene via magnesium carbenoid 1,3-C−H insertion.…”

Section: Other Cyclopropane Formation Methodsmentioning

confidence: 99%

Cyclopropanation

Yeung

Kwong

2011

Encyclopedia of Catalysis

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“…The same 1,3-CH insertion reaction was found to proceed with sulfoxides 32, which were derived from vinyl sulfoxides 31 with lithium enolate of carboxylic acid tert-butyl ester in high yields. 10 Thus, treatment of sulfoxides 32 with 2.5 equiv of i-PrMgCl in toluene resulted in the formation of bicyclo[n.1.0]alkanes 33 in high to quantitative yields. This type of reaction can be realized not only with tert-butyl ester but also with amides.…”

Section: -2 13-carbon Hydrogen (13-ch) Insertion Reactionmentioning

confidence: 99%

Recent Advances in the Chemistry and Synthetic Uses of Magnesium Carbenoids

Satoh¹

2012

HETEROCYCLES

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Carbenes and carbenoids have long been recognized to be a highly reactive species and are frequently used as intermediates in organic synthesis.However, most of the carbenes and carbenoids are relatively short-lived and are too reactive to control. Recently, the author's group found that the treatment of aryl -chloroalkyl sulfoxides and -chlorovinyl p-tolyl sulfoxides with a Grignard reagent at low temperature gave magnesium carbenoids via the sulfoxide-magnesium exchange reaction. Magnesium carbenoids, cyclopropylmagnesium carbenoids, cyclobutylmagnesium carbenoids, magnesium alkylidene carbenoids, and magnesium -oxido carbenoids were generated from the corresponding -chloro sulfoxides with a Grignard reagent at low temperature.The generated magnesium carbenoids were proved to be relatively stable and they showed very interesting reactivity with several nucleophiles to afford many unprecedented new reactions. The present review is written for the purpose of reflecting recent achievements in the areas of chemistry and synthetic application of above-mentioned magnesium carbenoids. This review mainly covers literature from 2006 to late 2011. CONTENTS1.

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A versatile synthesis, including asymmetric synthesis, of bicyclo[n.1.0]alkanes from cyclic ketones via the magnesium carbenoid 1,3-CH insertion as a key reaction

Cited by 38 publications

References 24 publications

Recent advances in the chemistry of magnesium carbenoids

Recent advances in the chemistry of magnesium carbenoids

Cyclopropanation

Recent Advances in the Chemistry and Synthetic Uses of Magnesium Carbenoids

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