Metal Bound or Free Ylides as Reaction Intermediates in Metal-Catalyzed [2,3]-Sigmatropic Rearrangements? It Depends,ACS Catalysis

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Metal Bound or Free Ylides as Reaction Intermediates in Metal-Catalyzed [2,3]-Sigmatropic Rearrangements? It Depends
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-01-04 , DOI: 10.1021/acscatal.0c04768
Croix J. Laconsay ₁ , Dean J. Tantillo ₁

Affiliation

Density functional theory calculations were applied to study four previously published metal-catalyzed [2,3]-rearrangements from onium ylide intermediates, in pursuit of generalizations about when, during these types of reactions, catalysts dissociate. Our results corroborate past studies where free-ylide mechanisms were proposed to be operative. Results of calculations on case studies indicate that the origin of metal–catalyst dissociation can be attributed primarily to the steric bulkiness of functional groups adjacent to the carbene carbon.

中文翻译：

金属结合的或游离的叶立德作为金属催化的[2,3]-σ重排反应的中间体？这取决于

应用密度泛函理论计算来研究四种以前发表的由金属鎓叶立德中间体产生的金属催化的[2,3]重排，以寻求关于在这些类型的反应中何时催化剂解离的概括。我们的研究结果证实了以前的研究，其中提出了有效的自由内酯作用机制。案例研究的计算结果表明，金属催化剂解离的起源可主要归因于与卡宾碳相邻的官能团的空间庞大。

更新日期：2021-01-15

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