Department of Chemistry, Davenport Chemical Laboratories, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada.
Carbogen Amcis AG, Hauptstraße 171, 4416, Bubendorf, Switzerland.
Angew Chem Int Ed Engl. 2017 May 22;56(22):6307-6311. doi: 10.1002/anie.201700632. Epub 2017 Mar 20.
Herein we describe a rhodium-catalyzed enantioselective isomerization of meso-oxabicyclic alkenes to 1,2-naphthalene oxides. These potentially useful building blocks can be accessed in moderate to excellent yields with impressive enantioselectivities. Additionally, experimental findings supported by preliminary computations suggest that ring-opening reactions of bridgehead disubstituted oxabicyclic alkenes proceed through the intermediacy of these epoxides and may point to a kinetically and thermodynamically favored reductive elimination as the origin for the observed enantioselectivities.
在此，我们描述了一种铑催化的对映选择性异构化反应，可将中氧杂双环烯烃转化为 1,2-萘氧氧化物。这些潜在有用的构建块可以以中等至优异的收率获得，对映选择性很高。此外，实验结果得到初步计算的支持，表明桥头双取代氧杂双环烯烃的开环反应是通过这些环氧化物中间体进行的，这可能表明观察到的对映选择性来源于动力学和热力学有利的还原消除。
