Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 31, Pages 11234-11241Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja904116k
Keywords
-
Categories
Funding
- NIH NIGMS [GM073836]
Ask authors/readers for more resources
This contribution describes the substrate scope and mechanism of Pd-catalyzed ligand-directed C-H arylation with diaryliodonium salts. This transformation was applied to the Synthesis of a variety of different biaryl products, using directing groups including pyridines, quinolines, pyrrolidinones, and oxazolidinones. Electronically and sterically diverse aryl groups (At) were transferred in high yield using iodine(III) reagents of general structure [Mes-I-Ar]BF4. Mechanistic investigations have been conducted that establish the kinetic order of the catalytic reaction in each component, determine the resting state of the catalyst and the iodine(III) reagent, quantify the electronic influence of the arylating reagent on the reaction rate, and establish the intra- and intermolecular 1 degrees H/D kinetic isotope effect. On the basis of these studies, this transformation is proposed to proceed via turnover-limiting oxidation of the Pd dimer [Pd(N similar to C)(OAc)](2) (N similar to C = 3-methyl-2-phenylpyridine) by [Mes-I-Ph]BF4. This mechanism implicates a bimetallic high oxidation state Pd species as a key catalytic intermediate. The significance of this and other aspects of the proposed mechanism are discussed in detail.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available