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Effects of Phosphorus Substituents on Reactions of α‐Alkoxyphosphonium Salts with Nucleophiles
Author(s) -
Goto Akihiro,
Otake Kazuki,
Kubo Ozora,
Sawama Yoshinari,
Maegawa Tomohiro,
Fujioka Hiromichi
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201200480
Subject(s) - nucleophile , steric effects , chemistry , reactivity (psychology) , phosphine , reagent , medicinal chemistry , organic chemistry , phosphorus , electronic effect , nucleophilic substitution , catalysis , medicine , alternative medicine , pathology
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.