Catalytic Intermolecular Ortho-Arylation of Phenols

• Published in: Journal of organic chemistry Vol. 68; no. 22; pp. 8669 - 8682
• Main Authors: Bedford, Robin B, Limmert, Michael E
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 31.10.2003; Amer Chemical Soc
• Subjects: Catalysis; Catalytic reactions; Chemistry; Chemistry, Organic; Exact sciences and technology; General and physical chemistry; Physical Sciences; Science & Technology; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; NAPHTHOLS; REACTIVITY; SUZUKI; C-BOND FORMATION; ACTIVATION; COMPLEXES; Organic phosphinite; Arylation; Rhodium complex; Catalytic reaction; Tertiary phosphine; Selectivity; Transition metal Complexes; Transesterification; Triphenylphosphine; Optimization; Cocatalyst; Phenols; Aromatic compound; Metalation; Intermolecular reaction; Chemical synthesis; Catalyst; Halogen Organic compounds
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo030157k

The use of rhodium catalysts such as [RhCl(PPh3)3] or [{RhCl(COD)}2] with PiPr2(OAr) or P(NMe2)3 co-catalysts allows the ortho-selective intermolecular arylation of phenols. The reaction proceeds via orthometalation of P-OAr groups and then transesterification liberates the product phenol. When 2-substituted phenols are used as substrates, [RhCl(PPh3)3]/iPr2(OAr) mixtures are typically the catalysts of choice, whereas for substrates without 2-substitution [{RhCl(COD)}2]/P(NMe2)3 mixtures tend to give better results.