Bulger Ana S, Turner Daniel W, Zhou Qingyang, Houk K N, Garg Neil K
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, United States.
Org Lett. 2024 May 3;26(17):3602-3606. doi: 10.1021/acs.orglett.4c01037. Epub 2024 Apr 22.
We report an experimental and computational investigation of the likely mechanism of a cascade reaction. The reaction involves an intramolecular Diels-Alder reaction, followed by a C-C bond cleavage, to afford a complex bridged bicyclic product. As multiple reaction pathways could be envisioned for the latter step, the mechanism of the C-C bond cleavage step was investigated. Two reasonable reaction pathways were evaluated. Both computations and experiments indicate that the C-C bond cleavage step proceeds by a retro-carbonyl-ene pathway rather than a retro-aldol pathway. This report underscores the synergy between computational and experimental studies and establishes the mechanism of an interesting complexity-generating transformation.
我们报告了对一种级联反应可能机制的实验和计算研究。该反应涉及分子内狄尔斯-阿尔德反应，随后是碳-碳键断裂，以生成一种复杂的桥连双环产物。由于可以设想后一步有多种反应途径，因此对碳-碳键断裂步骤的机制进行了研究。评估了两条合理的反应途径。计算和实验均表明，碳-碳键断裂步骤是通过逆羰基烯途径而非逆羟醛途径进行的。本报告强调了计算研究与实验研究之间的协同作用，并确定了一种有趣的产生复杂性转化的机制。
