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. 2017 Oct 1;8(10):6888-6892.
doi: 10.1039/c7sc02175e. Epub 2017 Aug 4.

α-Perfluoroalkyl-β-alkynylation of alkenes via radical alkynyl migration

Xinjun Tang  1 , Armido Studer  1
Affiliations

α-Perfluoroalkyl-β-alkynylation of alkenes via radical alkynyl migration

Xinjun Tang et al. Chem Sci. .

Abstract

Transition metal-free radical α-perfluoroalkylation with concomitant β-alkynylation of unactivated alkenes is presented. These cascades proceed via electron-catalysis and comprise a radical 1,4- or 1,5-alkynyl migration from tertiary propargylic alcoholates to secondary or tertiary C-radicals as the key step. Alkynyl migration leads to a ketyl radical anion that sustains the chain as a single electron transfer reducing reagent.

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Figures

Scheme 1
Scheme 1. Vicinal alkene difunctionalization comprising a perfluoroalkylation.
Scheme 2
Scheme 2. Variation of the radical acceptor and the perfluoroalkyl iodides. a3.6 equivalents of CF3I were added in two parts and the reaction time was 24 hours.
Scheme 3
Scheme 3. Proposed mechanism.
Scheme 4
Scheme 4. Follow-up chemistry.
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