title: para-C-H Borylation of Benzene Derivatives by a Bulky Iridium Catalyst.
abstract: A highly para-selective aromatic C-H borylation has been accomplished. By a new iridium catalyst bearing a bulky diphosphine ligand, Xyl-MeO-BIPHEP, the C-H borylation of monosubstituted benzenes can be affected with para-selectivity up to 91%. This catalytic system is quite different from the usual iridium catalysts that cannot distinguish meta- and para-C-H bonds of monosubstituted benzene derivatives, resulting in the preferred formation of meta-products. The para-selectivity increases with increasing bulkiness of the substituent on the arene, indicating that the regioselectivity of the present reaction is primarily controlled by steric repulsion between substrate and catalyst. Caramiphen, an anticholinergic drug used in the treatment of Parkinson's disease, was converted into five derivatives via our para-selective borylation. The present [Ir(cod)OH]2/Xyl-MeO-BIPHEP catalyst represents a unique, sterically controlled, para-selective, aromatic C-H borylation system that should find use in streamlined, predictable chemical synthesis and in the rapid discovery and optimization of pharmaceuticals and materials.
authors: †Graduate School of Science, ‡JST, ERATO, Itami Molecular Nanocarbon Project, and §Institute of Transformative Bio-molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya 464-8602, Japan.
authors: Yutaro
authors: Y
authors: Saito
authors: †Graduate School of Science, ‡JST, ERATO, Itami Molecular Nanocarbon Project, and §Institute of Transformative Bio-molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya 464-8602, Japan.
authors: Yasutomo
authors: Y
authors: Segawa
authors: †Graduate School of Science, ‡JST, ERATO, Itami Molecular Nanocarbon Project, and §Institute of Transformative Bio-molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya 464-8602, Japan.
authors: Kenichiro
authors: K
authors: Itami
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D001896:Boron Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D007495:Iridium / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D001555:Benzene Derivatives; D001896:Boron Compounds; D008024:Ligands; D009942:Organometallic Compounds; D007495:Iridium