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Toward a Predictive Understanding of Phosphine-Catalyzed [3 + 2] Annulation of Allenoates With Acrylate or Imine

Toward a Predictive Understanding of Phosphine-Catalyzed [3 + 2] Annulation of Allenoates With Acrylate or Imine

Zhaoyuan Yu, Zhichao Jin, Meng Duan, Ruopeng Bai, Yixin Lu, Yu Lan

J Org Chem. 2018 Sep 7;83(17):9729-9740.

PMID: 30113828

Abstract:

Both theoretical and experimental studies were performed to explore the mechanism, regioselectivity, and enantioselectivity of phosphine-catalyzed [3 + 2] annulation between allenoates and acrylate or imine. Using density functional theory computations, we predicted that the enantioselective determining step is the nucleophilic addition of acrylate or imine to the catalyst-activated allenoate. In the key step, we proposed two hydrogen bonding interaction models (intermolecular H-bond model and intramolecular H-bond model). For acrylate substrates, the reaction proceeds via the intramolecular H-bond model and the strong noncovalent interactions between the 2-naphthyl ester moiety lead to the re-face attack pathway being more favorable. For imine substrates, the intermolecular H-bond model operates. In the annulation process, the bulky n-propyl oriented toward a crowded, sterically demanding environment plays a significant role in asymmetric induction. The theoretical calculation results agreed with experimental observations, and these results provide valuable insight into catalyst design and understanding of mechanisms of related reactions.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP52684341	2-Naphthyl acrylate		52684-34-1	Price

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