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Synthesis 2008(17): 2669-2679  
DOI: 10.1055/s-2008-1067220
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Diastereo- and Enantioselective Reductive Aldol Addition of Vinyl Ketones via Catalytic Hydrogenation

Soo Bong Han, Abbas Hassan, Michael J. Krische*
University of Texas at Austin, Department of Chemistry and Biochemistry, 1 University Station A5300, Austin, TX 78712-0165, USA
Fax: +1(512)4718696; e-Mail: mkrische@mail.utexas.edu;
Further Information

Publication History

Received 29 February 2008
Publication Date:
06 August 2008 (online)

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Abstract

An overview of studies on hydrogenative reductive aldol addition is presented. By simply hydrogenating enones in the presence of aldehydes at ambient temperature and pressure, aldol adducts are generated under neutral conditions in the absence of any stoichiometric byproducts. Using cationic rhodium complexes modified by tri(2-furyl)phosphine, highly syn-diastereoselective reductive aldol additions of vinyl ketones are achieved. Finally, using novel monodentate TADDOL-like phosphonite ligands, the first highly diastereo- and enantioselective reductive aldol couplings of vinyl ketones were devised. These studies, along with other works from our laboratory, demonstrate that organometallics arising transiently in the course of catalytic hydrogenation offer byproduct-free alternatives to preformed organometallic reagents employed in classical carbonyl addition processes.

1 Introduction

2 Intramolecular Hydrogenative Aldol Addition

3 Intermolecular Hydrogenative Aldol Addition

4 Conclusion and Outlook

Key words

hydrogenation - rhodium - green chemistry - aldol - enantioselective catalysis

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40

Consistent with internal hydride delivery to the enone s-cis conformer through a six-centered transition structure, enones constrained in the s-trans configuration, such as cyclohexenone, do not participate in hydrogenative reductive aldol coupling.