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Synthesis 2005(8): 1205-1227  
DOI: 10.1055/s-2005-865315
REVIEW
© Georg Thieme Verlag Stuttgart · New York

N-Phosphinoylimines: An Emerging Class of Reactive Intermediates for Stereoselective Organic Synthesis

Steven M. Weinreb*, Robert K. Orr
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA
Fax: +1(814)8653292; e-Mail: smw@chem.psu.edu;
Further Information

Publication History

Received 21 January 2005
Publication Date:
13 April 2005 (online)

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Abstract

N-Phosphinoylimines have recently begun to attract significant attention from synthetic chemists for the preparation of nitrogen-containing molecules. Several methods have been developed for the synthesis, or in situ generation, of these reactive electrophilic species. N-Phosphinoylimines undergo a wide range of reactions, including nucleophilic additions and cycloadditions. These imines are also effective electrophiles in a number of diastereoselective and enantioselective reactions. An advantage of using N-phosphinoylimines is that the reaction products can be easily deprotected under mild acidic conditions, leading to amines. This review outlines the preparation and uses of N-phosphinoylimines with particular emphasis on their applications in stereoselective processes.

  • 1 Introduction

  • 2 Preparation of N-Phosphinoylimines

  • 3 Addition of Nucleophiles to N-Phosphinoylimines

  • 3.1 Heteroatom Nucleophiles

  • 3.2 Hydride

  • 3.3 Carbon Nucleophiles

  • 3.3.1 Addition of Organometallics

  • 3.3.2 Chiral Auxiliary-Controlled Addition of Organometallics

  • 3.3.3 Enantioselective Addition Using Chiral Ligands

  • 3.3.4 Mannich and Related Reactions

  • 3.3.5 Addition of Nitrile Anions

  • 3.3.6 Aza-Henry Reaction

  • 3.3.7 Aza-Baylis-Hillman Reaction

  • 3.3.8 Formation of Aziridines

  • 3.3.9 Miscellaneous Addition Reactions

  • 4 Cycloadditions and Pericyclic Reactions of N-Phosphinoylimines

  • 5 Oxidation of N-Phosphinoylimines to Oxaziridines

  • 6 Conclusion

Key words

imines - amines - diastereoselective synthesis - enantio­selective synthesis - chiral catalysts