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Synlett 2009(11): 1695-1712  
DOI: 10.1055/s-0029-1217363
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Development of Catalytic Asymmetric Intramolecular Cyclopropanation of α-Diazo-β-Keto Sulfones and Applications to Natural Product Synthesis

Masahiro Honma, Hiroyuki Takeda, Masashi Takano, Masahisa Nakada*
Department of Chemistry and Biochemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan
Fax: +81(3)52863240; e-Mail: mnakada@waseda.jp;
Further Information

Publication History

Received 16 January 2009
Publication Date:
12 June 2009 (online)

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Abstract

The catalytic asymmetric intramolecular cyclopropanation (CAIMCP) of α-diazo-β-keto sulfones developed in our laboratory and applications to the total synthesis of natural products are described. CAIMCP features (a) a wide applicability, not only to the preparation of bicyclo[n.1.0]alkanes and tricyclo[4.n.0.0]alkenes, but also to the enantioselective total synthesis of natural products, (b) the formation of highly crystalline products, which facilitate the production of enantiomerically pure synthetic intermediates, and (c) the generation of products with a variety of functionalities, such as cyclopropane, ketone, and sulfone, beneficial to the total synthesis of natural products.

1 Introduction

2 Preparation of Substrates

3 Synthesis of Carbocyclic Ring Systems by CAIMCP

3.1 Synthesis of the Bicyclo[3.1.0]hexane System by CAIMCP of α-Diazo-β-Keto Sulfones

3.2 Synthesis of the Bicyclo[3.1.0]hexane System with an Aryl Substituent by CAIMCP of α-Diazo-β-Keto Sulfones

3.3 Synthesis of the Bicyclo[3.1.0]hexane System by CAIMCP of α-Diazo-β-Keto Esters

3.4 Synthesis of the Bicyclo[4.1.0]hexane System by CAIMCP of α-Diazo-β-Keto Sulfones

3.5 Synthesis of Tricyclo[4.3.0.0]nonene and Tricyclo-[4.4.0.0]decene Systems by CAIMCP of α-Diazo-β-Keto Sulfones

3.6 Synthesis of the Tricyclo[4.4.0.0]decene System by CAIMCP of α-Diazo-β-Keto Esters

4 Applications of CAIMCP to Natural Product Synthesis

4.1 Enantioselective Total Synthesis of (-)-Malyngolide

4.2 Enantioselective Total Synthesis of (-)-Methyl Jasmonate

4.3 Enantioselective Total Synthesis of (+)-Digitoxigenin

4.4 Enantioselective Total Synthesis of (+)-Allocyathin B2

4.5 Enantioselective Total Synthesis of (-)-Erinacine B and (-)-Erinacine E

5 Conclusion

Key words

asymmetric catalysis - carbene complexes - diazo compounds - natural products - sulfones

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