title: The AZARYPHOS family of ligands for ambifunctional catalysis: syntheses and use in ruthenium-catalyzed anti-Markovnikov hydration of terminal alkynes.
abstract: The family of AZARYPHOS (aza-aryl-phosphane) phosphane ligands, containing a phosphine unit and sterically shielded nitrogen lone pairs in the ligand periphery, is introduced as a tool for developing ambifunctional catalysis by the metal center and nitrogen lone pairs in the ligand sphere. General synthetic strategies have been developed to synthesize over 25 examples of structurally diverse (6-aryl-2-pyridyl)phosphanes (ARPYPHOS), (6-alkyl-2-pyridyl)phosphanes (ALPYPHOS), 4,6-disubsituted 1,3-diazin-2-ylphosphanes or 1,3,5-triazin-2-ylphosphanes, quinazolinylphosphanes, quinolinylphosphanes, and others. The scalable syntheses proceed in a few steps. The incorporation of AZARYPHOS ligands (L) into complexes [RuCp(L)(2)(MeCN)][PF(6)] (Cp = cyclopentadienyl) gives catalysts for the anti-Markovnikov hydration of terminal alkynes of the highest known activities. Electronic and steric ligand effects modulate the reaction kinetics over a range of two orders of magnitude. These results highlight the importance of using structurally diverse ligand families in the process of developing cooperative ambifunctional catalysis by a metal and its ligand.
authors: Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany. lukas.hintermann@oc.rwth-aachen.de
authors: Lukas
authors: L
authors: Hintermann
authors: Tuan Thanh
authors: TT
authors: Dang
authors: Aurélie
authors: A
authors: Labonne
authors: Thomas
authors: T
authors: Kribber
authors: Li
authors: L
authors: Xiao
authors: Pance
authors: P
authors: Naumov