Halogen‐Substituted Mesoionic‐Carbene/Palladium Complexes for Catalytic Arylation of Aldehydes

Abstract

Various halogenated mesoionic‐carbene (MIC)‐coordinated palladium complexes (denoted as TAPs and e‐TAPs) were prepared using triazolylidene precursors that were synthesized in only two steps via a click reaction. Among the prepared complexes, 2‐Bromophenyl group substituted e‐TAP (Br‐e‐TAP) showed optimal catalytic activity for the arylation of aldehydes with arylboronic compounds. Additionally, the Br‐e‐TAP catalyst assisted in synthesizing a wide range of functionalized diarylmethanols and arylmethanols in 29–95% yields with loadings of 0.2–0.6 mol% Pd.

Silyloxymethylation of Aryl Halides via Metallaphotoredox Catalyzed Desulfinative Cross‐Coupling with Silyl Rongalite

“…For the preparation of oxymethylated arenes, the processes based on C1 feedstock has long been practiced making use of formaldehyde, [4] methanol, [5] CO, [6] and CO 2 [7] . In these reactions giving rise to arylmethanol products, C1 feedstock is typically employed as an electrophile for the formation of a C sp 2 −C sp 3 bond with a preformed [4a–e] or in situ generated [4f] σ‐aryl nucleophile. Different in modality are the Friedel‐Crafts [4g,h] and Minisci arylations, [5] in which arylmethanols are produced from π‐arenes without recurse to organometallic aryl nucleophiles.…”