Nickel-Catalyzed Three-Component Unsymmetrical Bis-Allylation of Alkynes with Alkenes: A Density Functional Theory Study
Tao Yu, Jingxuan Zhang, Guo Liu, Liangfei Duan, Kun V. Tian, Gregory A. Chass, Weihua Mu
TL;DR
This study uses computational methods to understand how a nickel catalyst helps create complex chemical structures from alkynes and alkenes.
Contribution
The paper provides a detailed DFT-based mechanistic analysis of a nickel-catalyzed three-component reaction for bis-allylation of alkynes.
Findings
The reaction proceeds through five sequential steps, with oxidative addition and reductive elimination as key steps.
The electrophilic/nucleophilic properties of substrates were predicted using Hirshfeld charges.
The third component and tBuOK additive are crucial for reaction efficiency and catalyst regeneration.
Abstract
Density functional theory (DFT) characterizations were employed to resolve the structural and energetic aspects and product selectivities along the mechanistic reaction paths of the nickel-catalyzed three-component unsymmetrical bis-allylation of alkynes with alkenes. Our putative mechanism initiated with the in situ generation of the active catalytic species [Ni(0)L2] (L = NHC) from its precursors [Ni(COD)2, NHC·HCl] to activate the alkyne and alkene substrates to form the final skipped trienes. This proceeds via the following five sequential steps: oxidative addition (OA), β-F elimination, ring-opening complexation, C-B cleavage and reductive elimination (RE). Both the OA and RE steps (with respective free energy barriers of 24.2 and 24.8 kcal·mol−1) contribute to the observed reaction rates, with the former being the selectivity-controlling step of the entire chemical transformation.…
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Taxonomy
TopicsCatalytic C–H Functionalization Methods · Catalytic Cross-Coupling Reactions · Asymmetric Hydrogenation and Catalysis