Pd-catalyzed regiodivergent arylation of cyclic allylboronates.

ABSTRACT: Two complementary regiodivergent Pd-catalyzed arylations of the lithium salts of 6-membered cyclic allylboronates are reported. The two systems provide access to products featuring a polysubstituted alkene and a boronic ester and are both compatible with a broad range of aryl bromides or heteroaryl bromides. When a (P,N) ligand is employed, a highly C1-selective arylation is favored. With the use of a Buchwald-type monophosphine ligand, a highly C3-selective arylation is favored. DFT calculations served to establish that a solvated dimer of the substrate is involved rather than a monomeric allylboronate. For the C3-arylation pathway, regioselectivity is governed mostly by steric factors during binding of the substrate to the metal center. A Curtin-Hammett equilibrium is cruci

SUBMITTER: Zhang C 

PROVIDER: S-EPMC12570269 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature