Mechanism of gold(I)-catalyzed rearrangements of acetylenic amine-N-oxides: computational investigations lead to a new mechanism confirmed by experiment.
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ABSTRACT:
SUBMITTER: Noey EL
PROVIDER: S-EPMC3262115 | biostudies-literature | 2012 Jan
REPOSITORIES: biostudies-literature
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Mechanism of gold(I)-catalyzed rearrangements of acetylenic amine-N-oxides: computational investigations lead to a new mechanism confirmed by experiment.
Noey Elizabeth L EL Luo Yingdong Y Zhang Liming L Houk K N KN
Journal of the American Chemical Society 20111222 2
Quantum mechanical studies of the mechanism of gold-catalyzed rearrangements of acetylenic amine-N-oxides to piperidinones or azepanones have revealed a new mechanism involving a concerted heteroretroene reaction, formally a 1,5 hydrogen shift from the N-alkyl groups to the vinyl position of a gold-coordinated methyleneisoxazolidinium or methyleneoxazinanium. Density functional calculations (B3LYP, B3LYP-D3) on the heteroretroene mechanism reproduce experimental regioselectivities and provide an ...[more]
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