摘要：KEYWORDS:Rh catalysis, Decarboxylation(反应类型)Carboxylates, Boroxines(原料), aryl alkane(产物), C(sp3)-C(sp2)(成键类型),P‑Trifluoromethyl Ph

转自：康龙化成

Configuration Retention in P‑Trifluoromethyl Phosphine Enabled Rh(I)-Catalyzed Decarbonylative Coupling of Carboxylates and Boroxines

Shouzhi Zhang, Bo Li, and Suhua Li*

School of Chemistry, IGCME, Sun Yat-Sen University, Guangzhou 510006, China

—J. Am. Chem. Soc.,2025

Recommended by Murong Xu_MC3

KEYWORDS: Rh catalysis, Decarboxylation(反应类型)Carboxylates, Boroxines (原料), aryl alkane(产物), C(sp3)-C(sp2) (成键类型), P‑Trifluoromethyl Phosphine, configuration retention, CO release (其他)

ABSTRACT: As compared with asymmetric catalysis, the memory of chirality provides another promising strategy to introduce chiral centers in light of numerous chiral starting materials that can be accessed. Decarboxylative coupling has become an important strategy for C−C or C−X bond formation over decades of development for its versatility and the low cost and structural diversity of carboxylic acids. However, the memory of chirality or more general configuration retention in this transformation has seldom been studied. Here, we report a novel π acceptor-type ligand P-trifluoromethyl phosphine enabled Rh(I)-catalyzed decarbonylative coupling of carboxylates and boroxines. The configuration of the α-carbon can be fully retained in this transformation for chiral, cis-, or trans-substrates. Several P-trifluoromethyl phosphine-Rh(I) carbonyl complexes were prepared and their v(CO) values were compared with known complexes, which indicated that the π-accepting property of the ligand is important to the decarbonylative reaction.

Design of novel P-trifluoromethyl Phosphines for Rh(I)-catalyzed Decarbonylative Coupling

Influence of Ligand Diversity

Reaction Scope of Aryl Boroxines and Aliphatic Carboxylates

Reaction Scope of Chiral and cis-Substrates

Prof. Suhua Li et al have developed a new π-acceptor ligand [3,5- (CF3)2C6H4]2PCF3 (L13) that significantly enhances the Rh(I)-catalyzed decarbonylative coupling reaction of rarely studied aliphatic carboxylates. Numerous examples have been presented to demonstrate the broad scope of this transformation and modularize the derivatization of various natural products. Configuration retentionwas realized with high fidelity in converting chiral, cis-, or trans-substrates to the corresponding products without inversion of the configuration. The π-accepting nature of the ligand, as confirmed by the v(CO) value in the IR data, is crucial for facilitating the release of COfrom the metal center, which in turn could promote the decarbonylation step. Additionally, the addition of valeronitrile is beneficial, as it may coordinate with rhodium, stabilize the complex, and prevent the recombination of CO.

来源：新浪财经