Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to PIII‐Stereogenic Compounds

Author:

Liu Jianjian1,Deng Rui1,Liang Xuyang1,Zhou Mali1,Zheng Pengcheng1,Chi Yonggui Robin12ORCID

Affiliation:

1. National Key Laboratory of Green Pesticide Key Laboratory of Green Pesticide and Agricultural Bioengineering Ministry of Education Guizhou University 550025 Guiyang China

2. School of chemistry, chemical engineering, and biotechnology Nanyang Technological University 637371 Singapore Singapore

Abstract

AbstractIntermolecular pnictogen bonding (PnB) catalysis has received increased interest in non‐covalent organocatalysis. It has been demonstrated that organic electron‐deficient pnictogen atoms can act as prospective Lewis acids. Here, we present a catalytic approach for the asymmetric synthesis of chiral PIII compounds by combining intramolecular PnB interactions and carbene catalysis. Our design features a pre‐chiral phosphorus molecule bearing two electron‐withdrawing benzoyl groups, resulting in the formation of a σ‐hole at the P atom. X‐ray and non‐covalent interaction (NCI) analysis indicate that the model substrates exhibit intrinsic PnB interaction between the oxygen atom of the formyl group and the phosphorus atom. This induces a conformational locking effect, leading to the crystallization of the phosphorus substrate in a preferred conformation (P212121 chiral group). Under the catalysis of N–heterocyclic carbene, the aldehyde moiety activated by the pnictogen bond selectively reacts with an alcohol to yield the corresponding chiral monoester/phosphorus product with excellent enantioselectivity. This Lewis acidic phosphorus center, aroused by the non‐polarized intramolecular pnictogen bond interaction, assists in conformational and selective regulations, providing unique opportunities for catalysis and beyond.

Funder

National Key Research and Development Program of China

National Natural Science Foundation of China

Publisher

Wiley

Cited by 2 articles. 订阅此论文施引文献 订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献

1. Pnictogen‐Bonding Enzymes;Angewandte Chemie;2024-09-05

2. Pnictogen‐Bonding Enzymes;Angewandte Chemie International Edition;2024-09-05

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