Palladium-catalyzed 1,1-alkynylbromination of alkenes with alkynyl bromides

Palladium-catalyzed 1,1-alkynylbromination of alkenes with alkynyl bromides

The palladium-catalyzed 1,1-alkynylbromination of terminal alkenes with a silyl-protected alkynyl bromide is reported. The method tolerates a diverse range of alkenes including vinylarenes, acrylates, and even electronically unbiased alkene derivatives to afford propargylic bromides regioselectively...

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Veröffentlicht in:Chemical science (Cambridge) 2021-09, Vol.12 (37), p.12326-12332
Hauptverfasser: Ano, Yusuke, Kawai, Natsuki, Chatani, Naoto
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Acrylates
Alkenes
Bromides
Chemistry
Palladium
Stereoselectivity
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creator Ano, Yusuke
Kawai, Natsuki
Chatani, Naoto
description The palladium-catalyzed 1,1-alkynylbromination of terminal alkenes with a silyl-protected alkynyl bromide is reported. The method tolerates a diverse range of alkenes including vinylarenes, acrylates, and even electronically unbiased alkene derivatives to afford propargylic bromides regioselectively. Mechanistic studies and DFT calculations indicate that the 1,1-alkynylbromination reaction proceeds via the migration of the Pd center followed by the formation of a π-allenyl Pd intermediate, leading to the stereoselective reductive elimination of the C(sp 3 )-Br bond at the propargylic positon. The first Pd-catalyzed 1,1-alkynylbromination of terminal alkenes using alkynyl bromides, which provides direct access to a variety of functionalized propargylic bromides without the need for an external brominating reagent, is reported.
doi_str_mv 10.1039/d1sc02873a
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subjects Acrylates
Alkenes
Bromides
Chemistry
Palladium
Stereoselectivity
title Palladium-catalyzed 1,1-alkynylbromination of alkenes with alkynyl bromides
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