Synlett 2019; 30(20): 2263-2267
DOI: 10.1055/s-0039-1690250
letter
© Georg Thieme Verlag Stuttgart · New York

Geminal Difunctionalization of Vinylarenes: Concise Synthesis of 1,3-Dioxolan-4-ones

Pandur Venkatesan Balaji
,
Department of Organic Chemistry, Indian Institute of Science, Bangalore-560012, Karnataka, India   Email: scn@iisc.ac.in
› Author Affiliations
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Publication History

Received: 08 August 2019

Accepted after revision: 22 October 2019

Publication Date:
06 November 2019 (online)


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Abstract

We report a straightforward method for the synthesis of five-membered 1,3-dioxolan-4-ones by an unprecedented oxidative alkene geminal difunctionalization strategy using α-hydroxy carboxylic acids. Under the geminal oxidative addition conditions, various substituted α-hydroxy carboxylic acids and styrenes containing a variety of substituents, including β-substituted styrenes, were effectively coupled regioselectively (anti-Markovnikov) with an isobutyl-substituted chiral α-hydroxy carboxylic acid, providing an annulation with excellent dia­­stereoselectivity. An aryl migration in the semipinacol rearrangement leading to geminal oxidative addition of the α-hydroxy carboxylic acids was confirmed by deuterium-labelling and control studies.

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