On the importance of leaving group ability in reactions of ammonium, oxonium, phosphonium, and sulfonium ylides

被引：91

作者：

Aggarwal, VK ^{[1
]}

Harvey, JN ^{[1
]}

Robiette, R ^{[1
]}

机构：

[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 34期

关键词：

density functional calculations; leaving group ability; onium compounds; sigmatropic rearrangement; ylides;

D O I：

10.1002/anie.200501526

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Chemical Equation Presented) What controls reactivity of ylides? Computational data show that reactivity in the reactions shown in the scheme is mainly determined by the leaving group ability of the onium group, and this decreases for both intrinsic and thermochemical reasons in the order O > S > N > P. The results are consistent with experimental observations and account for the dearth of examples of phosphorus ylides in these reactions. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：5468 / 5471

页数：4

共 41 条

[1] Synthesis and applications of chiral organoboranes generated from sulfonium ylides [J].

Aggarwal, VK ;

Fang, GY ;

Schmidt, AT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (06) :1642-1643

[2] Catalytic, asymmetric sulfur ylide-mediated epoxidation of carbonyl compounds: Scope, selectivity, and applications in synthesis [J].

Aggarwal, VK ;

Winn, CL .

ACCOUNTS OF CHEMICAL RESEARCH, 2004, 37 (08) :611-620

[3] Unraveling the mechanism of epoxide formation from sulfur ylides and aldehydes [J].

Aggarwal, VK ;

Harvey, JN ;

Richardson, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (20) :5747-5756

[4] SYNTHESIS OF SULFONIUM SALTS BY SULFIDE ALKYLATION - AN ALTERNATIVE APPROACH [J].

AGGARWAL, VK ;

THOMPSON, A ;

JONES, RVH .

TETRAHEDRON LETTERS, 1994, 35 (46) :8659-8660

[5]

BALDWIN JE, 1970, J CHEM SOC CHEM COMM, P631

[6]

BLACKBURN GM, 1968, J CHEM SOC CHEM COMM, V4, P186

[7] Migratory aptitudes of simple alkyl groups in the anionotropic rearrangement of quaternary chloromethyl borate species: A combined experimental and theoretical investigation [J].

Bottoni, A ;

Lombardo, M ;

Neri, A ;

Trombini, C .

JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (09) :3397-3405

[8]

CAREY FA, 1990, ADV ORGANIC CHEM

[9] Gas-phase ionic reactions: Dynamics and mechanism of nucleophilic displacements [J].

Chabinyc, ML ;

Craig, SL ;

Regan, CK ;

Brauman, JI .

SCIENCE, 1998, 279 (5358) :1882-1886

[10] Effects of adjacent onium cations and remote substituents on the H-A+ bond equilibrium acidities in dimethyl sulfoxide solution.: An extensive ylide thermodynamic stability scale and implication for the importance of resonance effect on ylide stabilities [J].

Cheng, JP ;

Liu, B ;

Zhao, YY ;

Sun, YK ;

Zhang, XM ;

Lu, Y .

JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (02) :604-610

← 1 2 3 4 5 →