ja1c13586_si_001.pdf (15.52 MB)
PdII–Catalyzed Site-selective β- and γ‑C(sp3)–H Arylation of Primary Aldehydes Controlled by Transient Directing Groups
journal contribution
posted on 2022-03-14, 22:43 authored by Yi-Hao Li, Yuxin Ouyang, Nikita Chekshin, Jin-Quan YuPd(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.