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Selectivity control in thiol-yne click reactions via visible light induced associative electron upconversion.

ABSTRACT: An associative electron upconversion is proposed as a key step determining the selectivity of thiol-yne coupling. The developed synthetic approach provided an efficient tool to access a comprehensive range of products - four types of vinyl sulfides were prepared in high yields and selectivity. We report practically important transition-metal-free regioselective thiol-yne addition and formation of the demanding Markovnikov-type product by a radical photoredox process. The photochemical process was directly monitored by mass-spectrometry in a specially designed ESI-MS device with green laser excitation in the spray chamber. The proposed reaction mechanism is supported by experiments and DFT calculations.

SUBMITTER: Burykina JV

PROVIDER: S-EPMC8162103 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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Selectivity control in thiol-yne click reactions <i>via</i> visible light induced associative electron upconversion.

Burykina Julia V JV Shlapakov Nikita S NS Gordeev Evgeniy G EG König Burkhard B Ananikov Valentine P VP

Chemical science 20200723 37

An associative electron upconversion is proposed as a key step determining the selectivity of thiol-yne coupling. The developed synthetic approach provided an efficient tool to access a comprehensive range of products - four types of vinyl sulfides were prepared in high yields and selectivity. We report practically important transition-metal-free regioselective thiol-yne addition and formation of the demanding Markovnikov-type product by a radical photoredox process. The photochemical process wa ...[more]

PMID: 34094267

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Visible light mediated metal-free thiol-yne click reaction.

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