摘要：Center of Basic Molecular Science (CBMS),Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China;

转自：康龙化成

Transition-Metal-Free Directα‑Arylation of Weinreb-type Amides with Arylboronic Acids through Aza-oxyallyl Cation Intermediates

Jiali Gao, Minmin Hu, Yuzhi Wang, Sanzhong Luo, and Xueling Mi*

College of Chemistry, Beijing NormalUniversity, Beijing 100875, P. R. China

Center of Basic Molecular Science (CBMS),Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China;

—J.Org. Chem. 2024, 89, 13730−13734

Recommended by Yuquan Liu_PT

KEYWORDS: α‑Arylation (反应类型), C(sp3)-C(sp2) (成键类型), Weinreb Amides (原料),aryl boronic acids (原料),HFIP (试剂), TransitionMetal Free (其他)

ABSTRACT: Here,the authors reported an efficient transition-metal-free C(sp2)-C(sp3)Suzuki-Miyaura-typecross-coupling between α-haloWeinreb-type amides and arylboronic acids. The reaction is carried out by capturing active aza-oxyallylcation (AOAC) with arylboronic acidto form a boron “ate” complex, followed by 1,4- migration to give α-aryl amides with good yields.

Selected substrate scope

Mechanistic studies

Prof. Xueling Mi etal described atransition-metal-free strategy for the preparation of α-aryl amides via Suzuki-Miyaura-typecross-coupling. The reaction proceeds through a 1,4-metalate shift of the boron “ate”complex between aza-oxyallylcation and boronic acid.This method shows a broad substrate scope and good functional group toleranceunder mild conditions. The simple, practical, and scalable approachdemonstrates its potential in preparing an array of pharmaceuticals andbioactive compounds.

来源：新浪财经