1-Aminopyridinium Ylides As Monodentate Directing Groups for Sp C-H Bond Functionalization

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2019 Sep 19

PMID 31529954

Citations 8

Authors

Ky Khac Anh Le

Hanh Nguyen

Olafs Daugulis

Affiliations

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Abstract

1-Aminopyridinium ylides are efficient directing groups for palladium-catalyzed β-arylation and alkylation of sp C-H bonds in carboxylic acid derivatives. The efficiency of these directing groups depends on the substitution at the pyridine moiety. The unsubstituted pyridine-derived ylides allow functionalization of primary C-H bonds, while methylene groups are unreactive in the absence of external ligands. 4-Pyrrolidinopyridine-containing ylides are capable of C-H functionalization in acyclic methylene groups in the absence of external ligands, thus rivaling the efficiency of the aminoquinoline directing group. Preliminary mechanistic studies have been performed. A cyclopalladated intermediate has been isolated and characterized by X-ray crystallography, and its reactivity was studied.

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