Asymmetric Cyclopropanations and Cycloadditions of Dioxocarbenes

Paul Müller; Yves F. Allenbach; Sabrina Chappellet; Ashraf Ghanem

doi:10.1055/s-2006-926452

SPECIALTOPIC

Asymmetric Cyclopropanations and Cycloadditions of Dioxocarbenes

Paul Müller*, Yves F. Allenbach, Sabrina Chappellet, Ashraf Ghanem
Department of Organic Chemistry, University of Geneva, 30 quai Ernest Ansermet, 1211 Geneva 4, Switzerland
Fax: +41(22)3793215; e-Mail: paul.muller@chiorg.unige.ch;

Abstract

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Abstract

Methods for enantioselective transfer of carbenes starting from precursors carrying two carbonyl groups have been elaborated. A one-pot procedure for olefin cyclopropanation with CH-acidic precursors via intermediate phenyliodonium ylides has been developed. The structure of the [Rh₂{(S)-nttl}₄] catalyst was optimized to produce up to 98% ee in olefin cyclopropanations with dimethyl malonate or Meldrum’s acid. Highly selective Rh(II)-catalyzed olefin cyclopropanations could be observed upon replacement of methyl diazoacetoacetate by methyl (silyloxy-vinyl)diazoacetate. Enantioselective dipolar cycloadditions of diazopyruvate to polar olefins have been realized with Ru(II)-pybox catalysts.

Key words

carbenoids - catalysis - diazo decomposition - phenyliodonium ylides - rhodium

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