title: Palladium-meta-terarylphosphine catalyst for the Mizoroki-Heck reaction of (hetero)aryl bromides and functional olefins.
abstract: The evolutionary meta-terarylphosphine ligand architecture of Cy*Phine was recently shown to be a key feature that imposed outstanding performance in palladium-catalyzed copper-free Sonogashira applications. Herein, the Pd-Cy*Phine combination has similarly proven to be a powerful catalyst system for the Mizoroki-Heck reaction. Using high-throughput screening (HTS) methodology, DMF and NaHCO3 were rapidly identified as the most effective solvent and base pair for the cross-coupling catalysis of challenging and industrially valuable substrates including highly electron-rich heteroaryl bromides and unactivated olefins. Unprotected functional groups were well tolerated using low catalyst loadings, and the simple protocol produced excellent yields (up to 99%) with unprecedented substrate diversity. The Pd-Cy*Phine system broadly outperformed many state-of-the-art commercial alternatives, which demonstrated its potential as a next-generation cross-coupling catalyst.
authors.affiliation: †Singapore Bioimaging Consortium (SBIC), Agency of Science, Technology and Research (A*STAR), 11 Biopolis Way, Helios, #01-02, Singapore 138667.
authors.forename: Daniel Weiliang
authors.initials: DW
authors.lastname: Tay
authors.forename: Howard
authors.initials: H
authors.lastname: Jong
authors.forename: Yee Hwee
authors.initials: YH
authors.lastname: Lim
authors.forename: Wenqin
authors.initials: W
authors.lastname: Wu
authors.forename: Xinying
authors.initials: X
authors.lastname: Chew
authors.affiliation: †Singapore Bioimaging Consortium (SBIC), Agency of Science, Technology and Research (A*STAR), 11 Biopolis Way, Helios, #01-02, Singapore 138667.
authors.forename: Edward G
authors.initials: EG
authors.lastname: Robins
authors.forename: Charles W
authors.initials: CW
authors.lastname: Johannes
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001965:Bromides / Q000737:chemistry*; D002384:Catalysis; D008024:Ligands; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*
chemical_list: D000475:Alkenes; D001965:Bromides; D008024:Ligands; D010165:Palladium