Regio-, Diastereo-, and Enantioselective Nitroso-Diels鈥揂lder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids
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- 作者：Jonathan Pous ; Thibaut Courant ; Guillaume Bernadat ; Bogdan I. Iorga ; Florent Blanchard ; G茅raldine Masson
- 刊名：Journal of the American Chemical Society
- 出版年：2015
- 出版时间：September 23, 2015
- 年：2015
- 卷：137
- 期：37
- 页码：11950-11953
- 全文大小：391K
- ISSN：1520-5126
文摘
Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels鈥揂lder 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鈥揂lder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.