Regio-, Diastereo-, and Enantioselective Nitroso-Diels–Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids
作者:Jonathan Pous、Thibaut Courant、Guillaume Bernadat、Bogdan I. Iorga、Florent Blanchard、Géraldine Masson
DOI:10.1021/jacs.5b08515
日期:2015.9.23
nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous
手性磷酸催化亚硝基芳烃与氨基甲酸酯-二烯的不对称亚硝基-Diels-Alder 反应以高产率得到顺式-3,6-二取代二氢-1,2-恶嗪,并具有优异的区域选择性、非对映选择性和对映选择性。有趣的是,我们观察到该催化剂不仅能够控制对映选择性,而且能够逆转非催化亚硝基-狄尔斯-阿尔德反应的区域选择性。DFT 计算证实了区域化学逆转和异步协调机制。