First ever observation of the intermediate of phosphonium salt and ylide hydrolysis: P-hydroxytetraorganophosphorane

被引：39

作者：

Byrne, Peter A. ^{[1
]}

Ortin, Yannick ^{[1
]}

Gilheany, Declan G. ^{[1
]}

机构：

[1] Univ Coll Dublin, Ctr Synth & Chem Biol, Dublin 4, Ireland

来源：

CHEMICAL COMMUNICATIONS | 2015年 / 51卷 / 06期

基金：

爱尔兰科学基金会;

关键词：

NUCLEAR-MAGNETIC-RESONANCE; P-31; NMR-SPECTROSCOPY; WITTIG REACTION; ALKALINE-HYDROLYSIS; PHOSPHINE OXIDES; HETEROARYLPHOSPHORUS COMPOUNDS; TOPOLOGICAL REPRESENTATION; NUCLEOPHILIC DISPLACEMENT; SUBSTITUTION REACTIONS; EQUILIBRIUM ACIDITIES;

D O I：

10.1039/c4cc08644a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

P-Hydroxytetraorganophosphorane, the long-postulated intermediate in phosphonium salt and ylide hydrolysis, has been observed and characterised by low temperature NMR, finally definitively establishing its involvement in these reactions. The results require modification of the previously accepted mechanism for ylide hydrolysis: P-hydroxy-tetraorganophosphorane is generated directly by 4-centre reaction of ylide with water.

引用

页码：1147 / 1150

页数：4

共 104 条

[1] NUCLEOPHILIC DISPLACEMENT ON PHOSPHORUS IN PHOSPHONIUM COMPOUNDS WHERE PHOSPHORUS IS PART OF 5- AND 6-MEMBERED HETEROCYCLES [J].

AKSNES, G ;

BERGESEN, K .

ACTA CHEMICA SCANDINAVICA, 1965, 19 (04) :931-&

[2]

Allen D. Q., 1972, J CHEM SOC, V1972, P63

[3] CHEMISTRY OF HETEROARYLPHOSPHORUS COMPOUNDS .6. ALKALINE-HYDROLYSIS OF 1-METHYLPYRROL-2-YL-METHYL AND 1-METHYLPYRROL-2-YL-METHYL-PHOSPHONIUM SALTS - COMPARISON WITH 2-FURYL, 2-THIENYL, PHENYL, AND RELATED HETEROARYLMETHYL AND BENZYL DERIVATIVES - RELATIVE STABILITIES OF FORMING CARBANIONS [J].

ALLEN, DW ;

HUTLEY, BG ;

MELLOR, MTJ .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1974, (14) :1690-1694

[4] CHEMISTRY OF HETEROARYLPHOSPHORUS COMPOUNDS .2. IMPORTANCE OF INDUCTIVE EFFECTS OF PRE-EQUILIBRIA IN ALKALINE-HYDROLYSIS OF HETEROARYLPHOSPHONIUM SALTS - PHOSPHORUS-31 NUCLEAR MAGNETIC-RESONANCE STUDIES [J].

ALLEN, DW ;

MELLOR, MTJ ;

HUTLEY, BG .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1972, (01) :63-&

[5] ALKALINE HYDROLYSIS OF SOME CYCLIC PHOSPHONIUM SALTS - RING-OPENING AND RING-EXPANSION REACTIONS [J].

ALLEN, DW ;

MILLAR, IT .

JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1969, (02) :252-&

[6] Synthesis and solvatochromism of some dipolar aryl-phosphonium and -phosphine oxide systems [J].

Allen, DW ;

Mifflin, JP ;

Skabara, PJ .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2000, 601 (02) :293-298

[7] SYNTHESIS AND REACTIONS OF 2,2'-BIPHENYLYLENEBISDIETHYLPHOSPHINE . FORMATION OF CYCLIC DIQUATERNARY DIBROMIDES WITH ALKYLENE DIBROMIDES AND NATURE AND PROBABLE MECHANISM OF THEIR THERMAL DECOMPOSITION [J].

ALLEN, DW ;

MILLAR, IT ;

MANN, FG .

JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1967, (19) :1869-+

[8]

Asknes G., 1962, ACTA CHEM SCAND, V16, P1426

[9] Observation of pseudorotamers of two unconstrained Wittig intermediates, (3RS,4SR)- and (3RS,4RS)-4-cyclohexyl-2-ethyl-3,4-dimethyl-2,2-diphenyl-1,2λ5-oxaphosphetane by dynamic 31P NMR spectroscopy:: Line-shape analyses, conformations, and decomposition kinetics [J].

Bangerter, F ;

Karpf, M ;

Meier, LA ;

Rys, P ;

Skrabal, P .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (41) :10653-10659

[10] ALKALINE DECOMPOSITION OF SOME UNSATURATED CYCLIC PHOSPHONIUM COMPOUNDS [J].

BERGESEN, K .

ACTA CHEMICA SCANDINAVICA, 1966, 20 (03) :899-&

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