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Pd^II-Catalyzed Site-selective β- and γ-C(sp³)-H Arylation of Primary Aldehydes Controlled by Transient Directing Groups.

ABSTRACT: Pd(II)-catalyzed site-selective β- and γ-C(sp³)-H arylation of primary aldehydes is developed by rational design of L,X-type transient directing groups (TDG). External 2-pyridone ligands are identified to be crucial for the observed reactivity. By minimizing the loading of acid additives, the ligand effect is enhanced to achieve high reactivities of the challenging primary aldehyde substrates. Site selectivity can be switched from the proximate to the relatively remote position by changing the bite angle of TDG to match the desired palladacycle size. Experimental and computational investigations support this rationale for designing TDG to potentially achieve remote site-selective C(sp³)-H functionalizations.

SUBMITTER: Li YH

PROVIDER: S-EPMC9084563 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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PdII-Catalyzed Site-selective β- and γ-C(sp3)-H Arylation of Primary Aldehydes Controlled by Transient Directing Groups.

Li Yi-Hao YH Ouyang Yuxin Y Chekshin Nikita N Yu Jin-Quan JQ

Journal of the American Chemical Society 20220314 11

Pd(II)-catalyzed site-selective β- and γ-C(sp3)-H arylation of primary aldehydes is developed by rational design of L,X-type transient directing groups (TDG). External 2-pyridone ligands are identified to be crucial for the observed reactivity. By minimizing the loading of acid additives, the ligand effect is enhanced to achieve high reactivities of the challenging primary aldehyde substrates. Site selectivity can be switched from the proximate to the relatively remote position by cha ...[more]

PMID: 35286807

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