Palladium-Catalyzed Intermolecular Acylation of Aryl Diazoesters with ortho-Bromobenzaldehydes

Yinghua Yu; Qianqian Lu; Gui Chen; Chunsen Li; Xueliang Huang

doi:10.1002/anie.201710317

Palladium-Catalyzed Intermolecular Acylation of Aryl Diazoesters with ortho-Bromobenzaldehydes

Angew Chem Int Ed Engl. 2018 Jan 2;57(1):319-323. doi: 10.1002/anie.201710317. Epub 2017 Dec 5.

Authors

Yinghua Yu¹, Qianqian Lu², Gui Chen¹, Chunsen Li², Xueliang Huang¹

Affiliations

¹ Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.

PMID: 29165904
DOI: 10.1002/anie.201710317

Abstract

In this work, we describe a palladium-catalyzed intermolecular O acylation of α-diazoesters with ortho-bromobenzaldehydes. The C(sp² )-H bond activation of the aldehyde is enabled by migratory insertion of a palladium carbene intermediate. The diazoesters act as modular three-atom units to build up key seven-membered palladacycles, which are transformed into a variety of isocoumarin derivatives upon reductive elimination. Mechanistic experiments and DFT calculations provide insight into the reaction pathway.

Keywords: acylation; carbene complexes; metallacycles; ortho-bromobenzaldehydes; palladium.

Publication types

Research Support, Non-U.S. Gov't