Molecule-induced homolysis versus "concerted oxenoid oxygen insertion" in the oxidation of organic compounds by dimethyldioxirane

被引：60

作者：

Bravo, A ^{[1
]}

Fontana, F ^{[1
]}

Fronza, G ^{[1
]}

Minisci, F ^{[1
]}

Zhao, LH ^{[1
]}

机构：

[1] Politecn Milan, Dipartimento Chim, I-20131 Milan, Italy

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 63卷 / 02期

关键词：

D O I：

10.1021/jo971226w

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Evidence for a molecule-induced homolysis of dimethyldioxirane by several classes of organic compounds (alkanes, alkenes, ethers, alcohols, aldehydes, iododerivatives) is reported. Carbon-centered radicals, arising from alkanes, ethers, and aldehydes, are trapped by CBrCl3 or protonated quinolines. The dramatic influence of oxygen in these reactions, as well as the formation of products of induced homolysis of the dioxirane by carbon-centered radicals (CH4, CH3OH, CH3COOCH3, ROCOCH3, CH3COOCH2COCH3), strongly supports a radical mechanism. With alkenes and iodo derivatives the induced homolysis would lead to diradical intermediates, whose very fast fragmentation would prevent detection, but circumstantial evidence supports a radical mechanism.

引用

页码：254 / 263

页数：10

共 48 条

[11] OXIDATION OF ALKYL AND ARYL IODIDES, PHENYLACETALDEHYDE AND ALKENES BY DIMETHYLDIOXIRANE - REACTION-PRODUCTS AND MECHANISM
BRAVO, A
FONTANA, F
FRONZA, G
MINISCI, F
SERRI, A
[J]. TETRAHEDRON LETTERS, 1995, 36 (38) : 6945 - 6948
[12] Radical versus ''oxenoid'' oxygen insertion mechanism in the oxidation of alkanes and alcohols by aromatic peracids. New synthetic developments
Bravo, A
Bjorsvik, HR
Fontana, F
Minisci, F
Serri, A
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (26) : 9409 - 9416
[13] Ingold-Fischer ''persistent radical effect'', solvent effect, and metal salt oxidation of carbon-centered radicals in the synthesis of mixed peroxides from tert-butyl hydroperoxide
Bravo, A
Bjorsvik, HR
Fontana, F
Liguori, L
Minisci, F
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (12) : 3849 - 3857
[14] On the triggering of free radical reactivity of dimethyldioxirane
Curci, R
Dinoi, A
Fusco, C
Lillo, MA
[J]. TETRAHEDRON LETTERS, 1996, 37 (02) : 249 - 252
[15] OXIDATION OF ACETALS, AN ORTHOESTER, AND ETHERS BY DIOXIRANES THROUGH ALPHA-CH INSERTION
CURCI, R
D'ACCOLTI, L
FIORENTINO, M
FUSCO, C
ADAM, W
GONZALEZNUNEZ, ME
MELLO, R
[J]. TETRAHEDRON LETTERS, 1992, 33 (29) : 4225 - 4228
[16] OXIDATIVELY ASSISTED NUCLEOPHILIC-SUBSTITUTION ELIMINATION OF ALKYL IODIDES IN ALCOHOLIC MEDIA - A FURTHER STUDY
DAVIDSON, RI
KROPP, PJ
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1982, 47 (10) : 1904 - 1909
[17] DEMONTELLANO O, 1986, CYTOCHROME P450 STRU
[18] REACTION OF C-60 WITH DIMETHYLDIOXIRANE - FORMATION OF AN EPOXIDE AND A 1,3-DIOXOLANE DERIVATIVE
ELEMES, Y
SILVERMAN, SK
SHEU, CM
KAO, M
FOOTE, CS
ALVAREZ, MM
WHETTEN, RL
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1992, 31 (03): : 351 - 353
[19] DECOMPOSITION OF DIOXIRANES INDUCED BY DIALKYL ETHERS
FERRER, M
SANCHEZBAEZA, F
CASAS, J
MESSEGUER, A
[J]. TETRAHEDRON LETTERS, 1994, 35 (18) : 2981 - 2984
[20] FISCHER H, 1986, J AM CHEM SOC, V108, P3925, DOI 10.1021/ja00274a012

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