Synthesis 2006(13): 2206-2214  
DOI: 10.1055/s-2006-942412
PAPER
© Georg Thieme Verlag Stuttgart · New York

Enantioselectivity and Diastereoselectivity in Reductive Radical Cyclization Reactions of 3-(ω-Iodoalkylidene)-piperidin-2-ones

Martina Dressel, Tobias Aechtner, Thorsten Bach*
Lehrstuhl für Organische Chemie I, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany
Fax: +49(89)28913315; e-Mail: thorsten.bach@ch.tum.de;
Further Information

Publication History

Received 27 April 2006
Publication Date:
08 June 2006 (online)

Abstract

The E-configurated 3-(ω-iodoalkylidene)-piperidin-2-ones 1a-e were prepared from the corresponding ω-tert-butyldi­methylsilyloxyalkanals 5a-e by aldol condensation with N-tert-butyloxycarbonylpiperidone, subsequent silyl deprotection and iodo-dehydroxylation. In the presence of tributylstannane as the reducing agent and of triethylborane as the initiator the iodides underwent a reductive radical cyclization to the corresponding products rac-9a-e (72-90% yield). The hydrogen abstraction occurred enantioselectively in the presence of the chiral complexing agent 2 in toluene as solvent (up to 88% ee). For substrates 1b and 1c, for which both the radical cyclization and the hydrogen abstraction step were stereogenic, the insignificant change in diastereoselectivity indicated that the cyclization step was not enantioselective. A 1:1 stoichiometry for the complex was proven by Job plot experiments. The enantioselectivity of the reaction 1a9a was concentration dependent.

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