Stereo- and Regioselective Alkyne Hydrometallation with Gold(III) Hydrides.
Angew Chem Int Ed Engl
; 55(40): 12321-4, 2016 09 26.
Article
em En
| MEDLINE
| ID: mdl-27592697
ABSTRACT
The hydroauration of internal and terminal alkynes by gold(III) hydride complexes [(C^N^C)AuH] was found to be mediated by radicals and proceeds by an unexpected binuclear outer-sphere mechanism to cleanly form trans-insertion products. Radical precursors such as azobisisobutyronitrile lead to a drastic rate enhancement. DFT calculations support the proposed radical mechanism, with very low activation barriers, and rule out mononuclear mechanistic alternatives. These alkyne hydroaurations are highly regio- and stereospecific for the formation of Z-vinyl isomers, with Z/E ratios of >991 in most cases.
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01-internacional
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MEDLINE
Idioma:
En
Ano de publicação:
2016
Tipo de documento:
Article