Aryl Migration Enables Vicinal Difunctionalization of Alkenes with Arylboronic Acids and Nucleophiles
左の本文を選ぶと、右側の官報原文画像で該当箇所を照合できます。
Aryl Migration Enables Vicinal Difunctionalization of Alkenes with Arylboronic Acids and Nucleophiles
Ying Xia, Guangbin Dong,* Jin Wang, Xuefeng Xu, Tianren Meng, Zhenhua Xu, and Qun Liu*
Cite This: J. Am. Chem. Soc. 2014, 136, 17641-17644
Read Online
ACCESS | Metrics & More Article Recommendations Supporting Information
ABSTRACT: A palladium-catalyzed vicinal difunctionalization of alkenes with arylboronic acids and nucleophiles has been developed. The reaction proceeds through a novel mechanism involving an aryl migration from boron to carbon. This method provides a new approach for the synthesis of complex molecules containing multiple functional groups.
T he development of efficient methods for the construction of C-C and C-heteroatom bonds is one of the most important tasks in organic synthesis. In particular, the vicinal difunctionalization of alkenes has attracted significant attention due to its potential for rapid access to complex molecular architectures. Traditional approaches often rely on prefunctionalized substrates or harsh reaction conditions. Herein, we report a novel palladium-catalyzed strategy that enables the direct vicinal difunctionalization of unactivated alkenes using readily available arylboronic acids and various nucleophiles.
The key feature of this transformation is the involvement of an unprecedented aryl migration step from boron to carbon, which occurs after the initial insertion of the alkene into the Pd-Ar bond. This mechanistic pathway distinguishes our method from conventional cross-coupling reactions and opens up new possibilities for synthetic design. We have demonstrated the broad scope of this reaction with respect to both the alkene and the nucleophile components, achieving high yields and excellent regioselectivity in many cases.
Furthermore, the reaction conditions are mild and compatible with a wide range of functional groups, making it suitable for late-stage functionalization of complex molecules. Detailed mechanistic studies, including kinetic isotope effect experiments and DFT calculations, support the proposed catalytic cycle involving aryl migration. This work not only provides a practical tool for organic synthesis but also expands the fundamental understanding of organoboron chemistry and palladium catalysis.