期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 134, 期 2, 页码 1078-1084出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja208860x
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资金
- National Institute of Health [T32GM008496]
- National Science Foundation [CHE-0548209]
- National Institute of General Medical Sciences, National Institutes of Health [R01 GM084254]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1059084] Funding Source: National Science Foundation
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 explanation as to why the hydrogen is transferred from the smaller amine substituent. In support of the proposed mechanism, new experimental investigations show that the hydrogen shift is concerted and that gold carbenes are not involved as reaction intermediates.
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