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J Am Chem Soc. 2016 Apr 27;138(16):5218-21. doi: 10.1021/jacs.6b01707. Epub 2016 Apr 18.

Utility of Ligand Effect in Homogenous Gold Catalysis: Enabling Regiodivergent π-Bond-Activated Cyclization.

Author information

1
Shanghai Key Laboratory of Green Chemistry and Chemical Process, School of Chemistry and Molecular Engineering, East China Normal University , 3663 North Zhongshan Road, Shanghai, 200062, P. R. China.
2
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, P. R. China.

Abstract

Comprehensive utilization of both electronic and steric properties of ligands in homogeneous gold catalysis is achieved in the regiodivergent intramolecular hydroarylation of alkynes. A flexible electron-deficient phosphite ligand, combined with the readily transformable directing group methoxyl amide, is attached to a cationic Au(I) center in three-coordinate mode, affording sterically hindered ortho-position cyclization. Meanwhile, para-position cyclization is exclusively achieved with the assistance of a rigid electron-abundant phosphine ligand-based Au(I) catalyst, in which ligands manifest the compensating effect for cyclization through steric hindrance and electronic properties. By combining gold with silver catalysts, tetrahydropyrroloquinolinones possessing a congested tricyclic structure are obtained via a proven Au/Ag relay catalytic process.

PMID:
27058740
DOI:
10.1021/jacs.6b01707

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