Issue 19, 2000
From the journal:

Journal of the Chemical Society, Perkin Transactions 1

Synthesis of α-hydroxy-β,β-difluoro-γ-ketoesters via [3,3]sigmatropic rearrangements

Michael J. Broadhurst,a   Samantha J. Brown,b   Jonathan M. Percy*b  and  Michael E. Prime†b  

* Corresponding authors

a Roche Discovery Welwyn, 40 Broadwater Road, Welwyn Garden City, Hertfordshire, UK

b School of Chemistry, The University of Birmingham, Edgbaston, Birmingham, UK

Abstract

Readily available γ,γ-difluorinated allylic alcohols obtained from trifluoroethanol were esterified efficiently. Exposure to strong base (LDA) afforded the ester enolates, in which chelation both controlled configuration and stabilised against fragmentation, which were trapped as their silyl ketene acetals. Rearrangement occurred to afford base-sensitive acid products. Esterification under mild conditions afforded the purifiable methyl esters in which the masked ketone had been released. Educts with either a benzyloxy or an allyloxy group at the α-position could be deprotected releasing the alcohols.

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Article information

DOI
https://doi.org/10.1039/B004766J
Article type
Paper
Submitted
14 Jun 2000
Accepted
31 Jul 2000
First published
11 Sep 2000

J. Chem. Soc., Perkin Trans. 1, 2000, 3217-3226

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Synthesis of α-hydroxy-β,β-difluoro-γ-ketoesters via [3,3]sigmatropic rearrangements

M. J. Broadhurst, S. J. Brown, J. M. Percy and M. E. Prime, J. Chem. Soc., Perkin Trans. 1, 2000, 3217 DOI: 10.1039/B004766J

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