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Highly active bifunctional salenTi(Ⅳ) catalysts for asymmetric cyanosilylation of aldehydes and TMSCN

Highly active bifunctional salenTi(Ⅳ) catalysts for asymmetric cyanosilylation of aldehydes and TMSCN
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摘要 A novel enantiopure salen ligand bearing a diphenylphosphine oxide on the 3-position of one aromatic ring was synthesized and combined with Ti(Oi-Pr)_4 as a monometallic bifunctional catalyst for asymmetric cyanosilylation reaction of aldehydes with tnmethylsilyl cyanide(TMSCN).The catalyst system exhibited excellent activity and moderate enantioselectivity.The addition of TMSCN to 4-nitrobenzaldehyde in the presence of 1 mol%catalyst loading could complete within 10 min at ambient temperature. An intramolecularly cooperative catalysis was observed in this system wherein the central metal Ti(Ⅳ) is suggested to play a role of Lewis acid to activate aldehydes while the appended diphenylphosphine oxide worked as Lewis base to activate TMSCN. A novel enantiopure salen ligand bearing a diphenylphosphine oxide on the 3-position of one aromatic ring was synthesized and combined with Ti(Oi-Pr)_4 as a monometallic bifunctional catalyst for asymmetric cyanosilylation reaction of aldehydes with tnmethylsilyl cyanide(TMSCN).The catalyst system exhibited excellent activity and moderate enantioselectivity.The addition of TMSCN to 4-nitrobenzaldehyde in the presence of 1 mol%catalyst loading could complete within 10 min at ambient temperature. An intramolecularly cooperative catalysis was observed in this system wherein the central metal Ti(Ⅳ) is suggested to play a role of Lewis acid to activate aldehydes while the appended diphenylphosphine oxide worked as Lewis base to activate TMSCN.
出处 《Chinese Chemical Letters》 SCIE CAS CSCD 2011年第11期1285-1288,共4页 中国化学快报(英文版)
基金 support by a Foundation for the Author of National Excellent Doctoral Dissertation of China(No FANEDD,200759)
关键词 Cyanohydnn Bifunctional catalyst SALEN TMSCN Diphenylphosphine oxide Cyanohydnn Bifunctional catalyst Salen TMSCN Diphenylphosphine oxide
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