Solvolysis of vinyl iodonium salts. New insights into vinyl cation intermediates

被引：132

作者：

Okuyama, T ^{[1
]}

机构：

[1] Himeji Inst Technol, Fac Sci, Kamigori, Hyogo 6781297, Japan

来源：

ACCOUNTS OF CHEMICAL RESEARCH | 2002年 / 35卷 / 01期

关键词：

D O I：

10.1021/ar0100374

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Solvolysis of some vinyl iodonium salts carrying an excellent leaving group is examined, focusing on whether or not a classical primary, vinyl cation can be generated. Formation of the primary cation is voided, when possible, by participation of the beta substituent in the heterolysis to form a vinylenebenzenium ion or a secondary vinyl cation. Definitive evidence against a primary vinyl cation is provided by a chirality, probe approach in the solvolysis of 4-methylcyclohexylidenemethyl iodonium salt.

引用

页码：12 / 18

页数：7

共 46 条

[1] TUNNELING SPLITTINGS IN THE ROTATIONAL SPECTRUM OF C2H3+ [J].

BOGEY, M ;

BOLVIN, H ;

CORDONNIER, M ;

DEMUYNCK, C ;

ESCRIBANO, R ;

GOMEZ, PC .

CANADIAN JOURNAL OF PHYSICS, 1994, 72 (11-12) :967-970

[2] GENERATION OF 2-SUBSTITUTED 1-ETHENYL CATIONS FROM ETHYLENEDIAZONIUM SALTS [J].

BOTT, K .

CHEMISCHE BERICHTE, 1994, 127 (05) :933-939

[3]

BOTT K, 1983, CHEM FUNCTIONAL GR C, P671

[4]

CHIAI M, 1991, J CHEM SOC CHEM COMM, P869

[5] INFRARED-SPECTROSCOPY OF CARBO-IONS .5. CLASSICAL VS NONCLASSICAL STRUCTURE OF PROTONATED ACETYLENE C2H-3+ [J].

CROFTON, MW ;

JAGOD, MF ;

REHFUSS, BD ;

OKA, T .

JOURNAL OF CHEMICAL PHYSICS, 1989, 91 (09) :5139-5153

[6] VINYLATION OF AROMATIC SUBSTRATES BY FREE UNSOLVATED VINYL CATION IN THE GASEOUS AND LIQUID-PHASE [J].

FORNARINI, S ;

SPERANZA, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (19) :7402-7407

[7] TRITIATED ETHYLENE AS PRECURSOR OF A FREE VINYL CATION [J].

FORNARINI, S ;

SPERANZA, M .

TETRAHEDRON LETTERS, 1984, 25 (08) :869-872

[8]

Fujita M, 2001, CHEM LETT, P806

[9] Chirality transfer from 4-methylcyclohexylidenemethyl(phenyl)iodonium tetrafluoroborate to 4-methylcycloheptanone during solvolysis: Evidence against a primary vinylic cation as intermediate [J].

Fujita, M ;

Sakanishi, Y ;

Okuyama, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (36) :8787-8788

[10] INFRARED-SPECTROSCOPY OF CARBOIONS .8. HOLLOW-CATHODE SPECTROSCOPY OF PROTONATED ACETYLENE, C2H3+ [J].

GABRYS, CM ;

UY, D ;

JAGOD, MF ;

OKA, T ;

AMANO, T .

JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (42) :15611-15623

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