Chemistry

Overcoming the inherent alkylation selectivity of 2,3-trans-3,4-cis- trisubstituted cyclopentanones

Document Type

Article

Abstract

Some ketones, especially 2,3-trans-3,4-cis-trisubstituted cyclopentanones, have strong inherent preferences to react through their less-substituted enolates, with neither kinetic nor thermodynamic conditions being able to selectively functionalize their more-substituted enolate isomers. Herein we report a synthetic strategy to overcome this limitation and selectively access the more-substituted alkylation products of these ketones. The strategy's key feature is to utilize a MeOCH2O group to temporarily block the more-reactive α position and to direct the ketone to react through its inherently less-reactive enolate isomer. The products formed by this strategy are useful synthetic intermediates on the path to multiple families of natural products. © Georg Thieme Verlag KG Stuttgart · New York.

Publication Title

Synthesis (Germany)

Publication Date

2-2014

Volume

46

Issue

3

First Page

387

Last Page

393

ISSN

0039-7881

DOI

10.1055/s-0033-1338573

Keywords

alkylation, ketones, natural products, neighboring-group effects, regioselectivity

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