Org Lett. 2026 Aug 14;28(32):10145-10150. doi: 10.1021/acs.orglett.6c01996.

ABSTRACT

A general and efficient P(III)-directed ruthenium-catalyzed C-H olefination of tertiary phosphines with alkenyl reagents is reported for modular synthesis of axially olefin-phosphines. This late-stage functionalization exhibits broad substrate scope for both phosphines and olefins. A diverse library of 55 olefin-phosphines was prepared in high yields, tolerating up to 15 different functional groups. These ligands demonstrate exceptional performance in Suzuki coupling, achieving catalyst loadings as low as 0.005 mol % and surpassing commercial biarylphosphines in facilitating Pd-catalyzed C-C and C-X bond formations. Mechanistic studies and DFT calculations support a Ru-C addition/β-bromo elimination pathway over oxidative addition.

PMID:42599436 | DOI:10.1021/acs.orglett.6c01996