期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 46, 页码 15943-15949出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b10008
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资金
- National Institutes of Health [R01GM110131]
- Deutsche Forschungsgemeinschaft [WI 4933/1-2]
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R01GM110131] Funding Source: NIH RePORTER
Identification of a novel catalyst-allenoate pair allows enantioselective [2+2] cycloaddition of alpha-methylstyrene. To understand the origin of selectivity, a detailed mechanistic investigation was conducted. Herein, two competing reaction pathways are proposed, which operate simultaneously and funnel the alkenes to the same axially chiral cyclobutanes. In agreement with the Woodward-Hoffmann rules, this mechanistic curiosity can be rationalized through a unique symmetry operation that was elucidated by deuteration experiments. In the case of 1,1-diarylalkenes, distal communication between the catalyst and alkene is achieved through subtle alteration of electronic properties and conformation. In this context, a Hammett study lends further credibility to a concerted mechanism. Thus, extended scope exploration, including beta-substitution on the alkene to generate two adjacent stereocenters within the cyclobutane ring, is achieved in a highly stereospecific and enantioselective fashion (33 examples, up to >99:1 er).
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