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Synthesis 2009(6): 869-887  
DOI: 10.1055/s-0028-1087980
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Stereoselective Transformations of meso Bicyclic Hydrazines: Versatile Access to Functionalized Aminocyclopentanes

Chloée Bournaud, Florence Chung, Alejandro Pérez Luna, Morgane Pasco, Gauthier Errasti, Thomas Lecourt, Laurent Micouin*
Laboratoire de Chimie Thérapeutique, UMR 8638 associée au CNRS et à l"Université Paris Descartes, Faculté des Sciences Pharmaceutiques et Biologiques 4, av de l’Observatoire, 75270 Paris cedex 06, France
Fax: +33(1)43291403; e-Mail: laurent.micouin@parisdescartes.fr;
Further Information

Publication History

Received 22 December 2008
Publication Date:
02 March 2009 (online)

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Abstract

Bicyclic hydrazines, prepared by cycloaddition of cyclopentadiene and diazo compounds, have great synthetic potential. Numerous asymmetric transformations of these building blocks have been developed, involving the electrophilicity of their strained double bond, ring-opening reactions or skeletal rearrangements. All these transformations are fully diastereoselective, and, in some cases­, enantioselective, enabling the preparation of a wide range of useful synthetic intermediates from a single precursor in a few synthetic steps.

1 Introduction

2 Preparation and Conformational Properties of Bicyclic
Hydrazines

3 Synthetic Transformations without Ring Fragmentation

3.1 Hydroboration

3.2 Hydroformylation and Halocarbomethoxylation

3.3 Dihydroxylation and Aminohydroxylation

3.4 Hydroarylation

3.5 Sequential Arylation-Alkynylation

3.6 Arylative Cyclization

3.7 Cyclopropanation

3.8 Pauson-Khand Reaction

3.9 Cycloaddition Reactions

4 Synthetic Transformations with Ring Fragmentation

4.1 Palladium-Catalyzed Ring-Opening Reactions

4.2 Copper-Catalyzed Ring-Opening Reactions

4.3 Rhodium-Catalyzed Ring-Opening Reactions

4.4 Ruthenium-Catalyzed Ring-Opening-Metathesis Reactions and Oxidative Cleavage

5 Rearrangements

5.1 Rearrangements Involving Allylic Cations

5.2 Rearrangements Involving Aziridiniums

6 Synthetic Applications

7 Conclusion

Key words

asymmetric synthesis - bicyclic hydrazines - ring-opening­ reactions - amines - asymmetric catalysis

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35

The low reactivity and selectivity observed with the QUINAP ligand could arise from the lower stability of the catalytic species generated from neutral rhodium precatalyst (Prof. J. M. Brown, personal communication to L.M.). Cationic rhodium sources have not been evaluated with this ligand in this study.

36

Pérez Luna, A.; unpublished results.

49

Bournaud, C.; unpublished results.