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Olefin and Cyclopropane Activation Through Geminal Phosphonium Centres
Schmidbaur, Hubert,Herr, Rudolf,Pollok, Thomas,Schier, Annette,Mueller, Gerhard,Riede, Juergen
, p. 3105 - 3113 (2007/10/02)
Complete quaternization of vinylidenebis(diphenylphosphane) (1) with CH3I or CH3OSO2F yields the diquaternary salts 2a, b, whose olefinic double bond is strongly electrophilic through the activation by two geminal phosphonium centres.Accordingly, addition of methanol or ethanol to 2a, b leads to β-alkoxy-substituted double phosphonium salts 9a-d.The structure of one of these products (9a: X=I, R=CH3) was elucidated by single crystal X-ray diffraction analysis.Spectroscopic data are provided for the remaining compounds. - Treatment of triphenylphosphonium cyclopropylide (5) with chlorodiphenylphosphane gives the gem-phosphino-substituted salt 6, which can be quaternized with CH3OSO2F to yield a bis-phosphonium salt (7a, b).A symmetrical homologue 7c is formed from cyclopropylidenebis(diphenylphosphane) (8) and CH3OSO2F.In 7a-c the cyclopropane cycle is also clearly activated.Ring cleavage occurs with alcohols leading to γ-alkoxylated salts 10a, b.
