Issue 13, 2024

Direct dehydroxy(sulfhydryl)xanthylation of alcohols and thiols

Abstract

Alkyl xanthates are broadly applied as synthetic intermediates for expedient access to a range of functional group derivatives in synthetic chemistry. Dehydroxyxanthylations of naturally rich alcohols are a promising approach but have rarely been explored mainly due to their challenging activation mode. Herein, we report the direct dehydroxyxanthylation of a wide range of primary and secondary alcohols via easily accessible and shelf-stable electrophilic N-xanthyl phthalimides under mild conditions, with superb functional group compatibility toward cyano and nitro groups, unprotected active groups (–NH2 and –OH), and double and triple bonds. The present organic halide-free protocol might provide a new and green avenue toward the synthesis of alkyl xanthates in an umpolung Mitsunobu-type manner in organic synthesis. Additionally, aliphatic thiols successfully undergo desulfhydrylxanthylation to produce the corresponding sp3C-xanthates. Notably, the xanthamide and thioxanthate groups could also be transformed to the desired alkyl substrates via this umpolung strategy. The broad substrate scope, excellent functional group compatibility and late-stage functionalization of bioactive molecules makes this protocol very attractive as a novel strategy for the rapid incorporation of SC(S)R (R = OEt, Oalkyl, NEt2 and SEt) onto the alkyl chains of complex systems.

Graphical abstract: Direct dehydroxy(sulfhydryl)xanthylation of alcohols and thiols

Supplementary files

Article information

Article type
Research Article
Submitted
05 Apr 2024
Accepted
10 May 2024
First published
13 May 2024

Org. Chem. Front., 2024,11, 3675-3684

Direct dehydroxy(sulfhydryl)xanthylation of alcohols and thiols

D. Shan, M. Jiang, F. Liang, Y. Zhong and D. Zhu, Org. Chem. Front., 2024, 11, 3675 DOI: 10.1039/D4QO00608A

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