期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 134, 期 40, 页码 16571-16577出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja303320x
关键词
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资金
- Enantioselective Synthesis Grant
- Canadian Society for Chemistry
- AstraZeneca Canada
- Boehringer Ingelheim (Canada) Ltd.
- Merck Frosst Canada
- NSERC collaborative R D program
- University of Ottawa
- Canadian Foundation for Innovation
- Ontario Ministry of Research and Innovation
- NSERC
- AstraZeneca
- American Chemical Society Petroleum Research Fund
- Boehringer Ingelheim (Canada) Ltd
Mechanistic investigations on the aldehyde-catalyzed intermolecular hydroamination of allylic amines using N-alkylhydroxylamines are presented. Under the reaction conditions, the presence of a specific aldehyde catalyst allows formation of a mixed aminal intermediate, which permits intramolecular Cope-type hydroamination. The reaction was determined to be first-order in both the aldehyde catalyst (alpha-benzyloxyacetaldehyde) and the allylic amine. However, the reaction displays an inverse order behavior in benzylhydroxylamine, which reveals a significant off-cycle pathway and highlights the importance of an aldehyde catalyst that promotes a reversible aminal formation. Kinetic isotope effect experiments suggest that hydroamination is the rate-limiting step of this catalytic cycle. Overall, these results enabled the elaboration of a more accurate catalytic cycle and led to the development of a more efficient catalytic system for alkene hydroamination. The use of 5-10 mol % of paraformaldehyde proved more effective than the use of 20 mol % of a-benzyloxyacetaldehyde, leading to high yields of intermolecular hydroamination products within 24 h at 30 degrees C.
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