Synthesis 2010(3): 365-388  
DOI: 10.1055/s-0029-1218601
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Catalytic Asymmetric Michael Additions of α-Cyanoacetates

Sascha Jautze, René Peters*
Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
Fax: +49(711)68564321; e-Mail: rene.peters@oc.uni-stuttgart.de;
Further Information

Publication History

Received 14 August 2009
Publication Date:
11 December 2009 (online)

Abstract

Enantiopure Michael addition products of α-cyanoacetates constitute attractive precursors for functionalised quaternary amino acids and other biologically interesting compounds. Since the pioneering work by Ito et al. in 1992 using rhodium(I) in combination with a trans-chelating planar chiral diphosphine, various complementary approaches have been reported; these are critically discussed and compared in this review. The most efficient recent methodologies utilise a bifunctional activation mode; for example, by dinuclear Lewis acid catalysis or by a well-defined hydrogen-bonding network. This strategy can overcome the difficulty that α-cyanoacetates are incapable of two-point binding to a Lewis acid thus hampering the differentiation of prochiral enol(ate) faces.

1 Introduction

2 Rhodium, Iridium and Ruthenium Catalysts

3 Palladium and Platinum Catalysts

4 Aluminium Catalysts

5 Organocatalysis

5.1 Cinchona Alkaloids

5.2 Thiourea-Derived Catalysts

5.3 Cinchona Alkaloid-(Thio)Urea Hybrids

5.4 Iminium Catalysis

6 Phase-Transfer Catalysis

7 Conclusions

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15

While the market price for a troy ounce (˜31.1 g) of Pd was roughly 190$ in March 2009, prices for Rh vary a lot and peaked at more than 6000$ in 2008 and reached about 1000$ in March 2009.

24

A promotion of the turnover of aluminium enolate intermediates is a likely role for the t-BuOH.