Issue 8, 2021

Understanding the sigmatropic shifts of cyclopenta-2,4-dien-1-yltrimethylsilane in its Diels–Alder addition

Abstract

To understand its dynamic processes in the Diels–Alder addition, temperature-dependent dynamic processes of cyclopenta-2,4-dien-1-yltrimethylsilane [1-(C5H5)Si(Me)3] are investigated by DFT computations. The degenerate sigmatropic migration of Si(Me)3 is found to be the dominant factor with a Gibbs free energy of activation of 13.2 kcal mol−1. The contribution from suprafacial hydrogen shifts is negligible, and the antarafacial sigmatropic hydrogen shifts are excluded due to their relatively high Gibbs barriers. Thermodynamically controlled Diels–Alder addition is obtained, which involves the critical interconversion between the 2,4-dienyl isomer 1 and 1,4-dienyl isomer 3.

Graphical abstract: Understanding the sigmatropic shifts of cyclopenta-2,4-dien-1-yltrimethylsilane in its Diels–Alder addition

Supplementary files

Article information

Article type
Communication
Submitted
30 nov. 2020
Accepted
29 janv. 2021
First published
29 janv. 2021

Org. Biomol. Chem., 2021,19, 1732-1737

Understanding the sigmatropic shifts of cyclopenta-2,4-dien-1-yltrimethylsilane in its Diels–Alder addition

M. Zhang and G. Liang, Org. Biomol. Chem., 2021, 19, 1732 DOI: 10.1039/D0OB02386H

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