Synthesis 2007(3): 355-362  
DOI: 10.1055/s-2006-958976
PAPER
© Georg Thieme Verlag Stuttgart · New York

Rearrangement of Homoallylic Alcohols with Thallium(III): Diastereoselective Synthesis of Indans Bearing a β-Hydroxy Ketone Moiety

Jr. Luiz F. Silva*, Samir A. P. Quintiliano, Marcus V. Craveiro, Fabiana Y. M. Vieira, Helena M. C. Ferraz
Instituto de Química, Universidade de São Paulo, CP 26077, CEP 05513-970, São Paulo SP, Brazil
e-Mail: luizfsjr@iq.usp.br;
Further Information

Publication History

Received 14 July 2006
Publication Date:
08 January 2007 (online)

Abstract

Several aspects of the synthesis of indans through a thallium(III)-mediated ring contraction reaction of 1,2-dihydronaphthalene derivatives bearing suitably positioned primary and secondary hydroxyl groups are disclosed. The relative configuration of 3-(2,3-dihydro-1H-inden-3-yl)-2-methyl-3-oxopropyl 4-bromobenzoate was assigned by X-ray crystal structure analysis, allowing additional insights into the mechanism of the thallium(III)-promoted oxidative rearrangement of homoallylic alcohols. The reaction of primary homoallylic alcohols bearing the electron-withdrawing group bromine gave indans in 52-55% yield using an excess of thallium trinitrate (TTN). Furthermore, the thallium(III)-mediated oxidative rearrangement of the secondary homoallylic alcohols gave, in a dia­stereoselective fashion, indans bearing up to three stereocenters.

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It is important to note that the products of the reaction (indans 12 and 13) are also prone to oxidation by thallium(III).

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The X-ray data have been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition number CCDC 618861.