Ti(III)-Mediated Radical-Induced Approach to a Bicyclic -Lactone with a Bridgehead beta-Hydroxy Group

Das, Dipendu and Khan, Hina P A and Chakraborty, Tushar Kanti (2018) Ti(III)-Mediated Radical-Induced Approach to a Bicyclic -Lactone with a Bridgehead beta-Hydroxy Group. In: SYNTHESIS-STUTTGART, 50 (15). pp. 3006-3014.

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Abstract

Herein, we portray a synthetic route to a bicyclic lactone containing a bridgehead hydroxy group, a structure that is present in many natural products of biological and medicinal relevance. Ethyl ( E )-3-(dimethylphenylsilyl)-7,8-epoxyoct-2-enoate underwent radical-mediated reductive epoxide opening with concomitant intramolecular cyclization using Cp (2) Ti(III)Cl to give cis -6-(dimethylphenylsilyl)-3-oxabicyclo4.3.0]nonan-4-one, a bicyclic lactone with a bridgehead silyl group serving as a masked hydroxy group. Furthermore, the bridgehead C-Si bond underwent stereoretentive oxidative cleavage to give cis -6-hydroxy-3-oxabicyclo4.3.0]nonan-4-one in high yield under Tamao-Fleming oxidation conditions; this demonstrates the potential utility of this strategy in the synthesis of many natural products bearing similar hydroxylated bridgehead chiral center embedded in a bicyclic lactone framework.

Item Type:	Journal Article
Publication:	SYNTHESIS-STUTTGART
Publisher:	GEORG THIEME VERLAG KG, RUDIGERSTR 14, D-70469 STUTTGART, GERMANY
Additional Information:	Copyright of this article belong to GEORG THIEME VERLAG KG, RUDIGERSTR 14, D-70469 STUTTGART, GERMANY
Department/Centre:	Division of Chemical Sciences > Organic Chemistry
Date Deposited:	08 Aug 2018 16:25
Last Modified:	08 Aug 2018 16:25
URI:	http://eprints.iisc.ac.in/id/eprint/60369

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