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Synlett 2014; 25(4): 466-476
DOI: 10.1055/s-0033-1340472
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© Georg Thieme Verlag Stuttgart · New York

Adventures in Ring-Contraction Reactions

Luiz F. Silva Jr.*
Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, Av. Prof. Lineu Prestes 748, CP 26077, CEP 05513-970 São Paulo SP, Brazil   Fax: +55(128)155579   Email: luizfsjr@iq.usp.br
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Publication History

Received: 28 October 2013

Accepted after revision: 21 November 2013

Publication Date:
13 January 2014 (online)

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Dedicated to Joaquim L. Matheus for 20 years of tremendous help in the lab.

Abstract

Nearly two decades of work on ring-contraction reactions is discussed in this account. We have developed several reliable protocols for the rearrangement of a number of different substrates using thallium(III) salts and, more recently, hypervalent iodine(III) reagents. A variety of ring systems, such as cyclopentanes, cis- and trans-hydrindanes, and indanes, can be obtained using these methods. Additionally, the stereoselective total syntheses of the sesquiterpenes (±)-, (–)- and (+)-mutisianthol and (+)-bakkenolide A, the indole alkaloid (±)- and (+)-trans-trikentrin A, and the potential drug (±)-indatraline have been achieved through a ring-contraction approach.

1 Introduction

2 Ring-Contraction Reactions Promoted by Thallium(III)

2.1 Thallium(III)-Mediated Ring Contraction of Cyclic Ketones

2.2 Thallium(III)-Mediated Ring Contraction of Cyclic Olefins

2.3 Thallium(III)-Mediated Ring Contraction of Homoallylic Alcohols

3 Ring-Contraction Reactions Promoted by Iodine(III)

4 Conclusion

Key words

total synthesis - ring contractions - oxidative rearrangements - thallium(III) - hypervalent iodine