The Inverse Demand Oxa-Diels–Alder Reaction of Resorcinarenes: An Experimental and Theoretical Analysis of Regioselectivity and Diastereoselectivity
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- 作者：Karolina Stefańska ; Hanna Jędrzejewska ; Michał Wierzbicki ; Agnieszka Szumna ; Waldemar Iwanek
- 刊名：Journal of Organic Chemistry
- 出版年：2016
- 出版时间：July 15, 2016
- 年：2016
- 卷：81
- 期：14
- 页码：6018-6025
- 全文大小：622K
- 年卷期：0
- ISSN：1520-6904
文摘
The Diels–Alder reaction enables introduction of new functionalities onto the resorcinarene skeleton with simultaneous generation of new stereogenic centers and expansion of the internal cavity. We present highly regio- and diastereoselective inverse electron demand oxa-Diels–Alder reactions of resorcinarene ortho-quinone methide with benzofuran and indene, each generating 12 new stereogenic centers. The mechanism and reasons for regioselectivity and diastereoselectivity were analyzed using theoretical calculations (NBO charges, Fukui functions, transition state energies, and thermodynamic stability of the products). Enantiomers were separated, and their configurations were determined by comparison of experimental and theoretical electronic circular dichroism spectra.