Synthesis of functionalized cyclopentanes, cyclohexanes and cycloheptanes by a silicon-induced domino reaction

authored by

Tycho Michel, Andreas Kirschning, Christian Beier, Nico Bräuer, Ernst Schaumann, Gunadi Adiwidjaja

Abstract

1,3-Functionalized cyclopentanes, -hexanes and -heptanes are obtained by addition of lithiated silyldithioacetals 7 to epoxyhomoallyl tosylates 4-6. The reaction involves a cascade of epoxide ring opening, of Brook 1,4-rearrangement and tosylate substitution. The method is particularly suitable for the preparation of cyclopentanes, whereas cyclohexanes and -heptanes are formed in yields only up to 49%. Use of enantiomerically pure epoxides provides optically active cyclopentanes (S)-10b, d, 11a as well as oxetanes (S)-14a, b. Hydrolysis of the dithioacetal function leads to the corresponding ketones 12. Cyclization of epoxide 24b gives an anellated cyclopentane 26, the configuration of which was established by X-ray structural analysis of dinitrobenzoate 27. Use of epoxide 29b provides the anellated tetrahydrofuran 30.

External Organisation(s)

Clausthal University of Technology
Universität Hamburg

Type

Article

Journal

Liebigs Annales

Pages

1811-1821

No. of pages

11

ISSN

0947-3440

Publication date

22.10.1996

Publication status

Published

Peer reviewed

Yes

ASJC Scopus subject areas

General Chemistry

Electronic version(s)

https://doi.org/10.1002/jlac.199619961115 (Access: Unknown)