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Synthesis 2003(8): 1137-1156
DOI: 10.1055/s-2003-39389
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Selectivity in Rhodium(II) Catalyzed Reactions of Diazo Compounds: Effects of Catalyst Electrophilicity, Diazo Substitution, and Substrate Substitution. From Chemoselectivity to Enantioselectivity

Craig A. Merlic*, Andrea L. Zechman
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive, Los Angeles, California 90095-1569
Fax: +1(310)2063722; e-Mail: Merlic@chem.ucla.edu;
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Publication History

Received 9 December 2002
Publication Date:
26 May 2003 (online)

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Abstract

Rhodium catalyzed reactions of diazo compounds form a powerful set of tools for synthetic organic chemists. Reactivity modes include cyclopropanation, C-H insertion, X-H insertion, and ylide formation. A myriad of factors influences the mode of reaction, selectivity, and yield for these reaction processes. This review examines the subtle electronic, steric and conformational effects that in turn have profound impacts on reaction paths and selectivity.

  • 1 Introduction

  • 2 Achiral Rhodium(II) Catalysts

  • 2.1 Effect of Catalyst Electrophilicity on Selectivity

  • 2.2 Effect of Diazo Substitution on Selectivity

  • 2.3 Effect of Substrate Substitution on Selectivity

  • 3 Chiral Rhodium(II) Catalysts

  • 3.1 Carboxylate Ligands

  • 3.2 Carboxamidate Ligands

  • 3.3 Phosphate Ligands

  • 3.4 Phosphine Ligands

  • 4 Conclusions

Key words

rhodium - catalysis - - carbenoids - stereoselective synthesis - diazo compounds