title: Effects of phosphorus substituents on reactions of α-alkoxyphosphonium salts with nucleophiles.
abstract: The effects of phosphorus substituents on the reactivity of α-alkoxyphosphonium salts with nucleophiles has been explored. Reactions of α-alkoxyphosphonium salts, prepared from various acetals and tris(o-tolyl)phosphine, with a variety of nucleophiles proceeded efficiently. These processes represent the first examples of high-yielding nucleophilic substitution reactions of α-alkoxyphosphonium salts. The reactivity of these salts was determined by a balance between steric and electronic factors, respectively, represented by cone angles θ and CO stretching frequencies ν (steric and electronic parameters, respectively). In addition, a novel reaction of α-alkoxyphosphonium salts derived from Ph(3)P with Grignard reagents was observed to take place in the presence of O(2) to afford alcohols in good yields. A radical mechanism is proposed for this process that has gained support from isotope-labeling and radical-inhibition experiments.
authors: Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka, Suita, Osaka, 565-0871 Japan.
authors: Akihiro
authors: A
authors: Goto
authors: Kazuki
authors: K
authors: Otake
authors: Ozora
authors: O
authors: Kubo
authors: Yoshinari
authors: Y
authors: Sawama
authors: Tomohiro
authors: T
authors: Maegawa
authors: Hiromichi
authors: H
authors: Fujioka
mesh_terms: D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D012492:Salts / Q000737:chemistry
chemical_list: D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D012492:Salts; D010758:Phosphorus