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Insights into Lewis base-catalyzed chemoselective [3 + 2] and [3 + 4] annulation reactions of MBH carbonates

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Abstract

Predicting the chemoselectivity of Lewis base-catalyzed annulations of Morita–Baylis–Hillman (MBH) carbonates is one of the most challenging questions in the organocatalysis field. The origin of chemoselectivity in Lewis base-catalyzed [3 + 4] and [3 + 2] annulations of MBH carbonates was theoretically explored in this work. The calculated results indicate that the general reaction pathway contains five steps: (1) nucleophilic addition on the α-carbon of MBH carbonates by a Lewis base, (2) dissociation of BocO, (3) deprotonation of the α-carbon, (4) Michael addition, and (5) ring closure coupled with the dissociation of the Lewis base. The ring-closure step determines the chemoselectivity for the possible [3 + 4] and [3 + 2] annulation reactions. The chemoselectivity can be well predicted using frontier molecular orbital (FMO) analyses, which demonstrate that the different overlap modes of FMOs involved in ring-closure transition states control the chemoselectivity.

Graphical abstract: Insights into Lewis base-catalyzed chemoselective [3 + 2] and [3 + 4] annulation reactions of MBH carbonates

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Article information


Submitted
18 Apr 2020
Accepted
03 Jun 2020
First published
04 Jun 2020

Org. Chem. Front., 2020, Advance Article
Article type
Research Article

Insights into Lewis base-catalyzed chemoselective [3 + 2] and [3 + 4] annulation reactions of MBH carbonates

Q. Deng, S. Li, D. Wei and Y. Lan, Org. Chem. Front., 2020, Advance Article , DOI: 10.1039/D0QO00457J

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