TRIS(ARYL)AMINIUM HEXACHLOROANTIMONATES - CONVENIENT ONE-ELECTRON OXIDANTS FOR CHEMICAL ELECTRON-TRANSFER WITH BICYCLIC AZOALKANES AND BICYCLO[2.1.0]PENTANES

被引：11

作者：

ADAM, W

SAHIN, C

机构：

[1] Institut für Organische Chemie der Universität Würzburg, D-97074 Würzburg, Am Hubland

来源：

TETRAHEDRON LETTERS | 1994年 / 35卷 / 48期

关键词：

D O I：

10.1016/0040-4039(94)88418-8

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Treatment of the parent and bridgehead-substituted 2,3-diazabicyclo[2.2.1]hept-2-enes (1a-d) and their bicyclo[2.1.0]penranes (2a-d) with catalytic amounts (2-10 mol%) of tris(aryl)aminium hexachloroantimonates afforded the corresponding cyclopentenes (3a-d). A reversal in the regioselectivity of the 1,2 migration was observed for the unsymmetrical derivatives of bicyclo[2.1.0]pentane, namely 2b (methyl substitution) versus 2c (phenyl substitution). This surprising fact is rationalized in terms of delocalization of the positive charge into the aromatic ring for the 1,3-diyl radical cation, as corroborated by AM1 calculations.

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页码：9027 / 9030

页数：4

相关论文

共 22 条

[1] REACTION OF SOME PYRAZOLINES SUBSTITUTED BY 2 ELECTROMAGNETIC GEMINATED GROUPS WITH CE(NH4)2(NO3)6 - NEW SYNTHESIS OF ELECTROPHILIC 2-PYRONES [J].

ABDALLAH, H ;

GREE, R ;

CARRIE, R .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1985, 63 (11) :3031-3036

[2] PHOTOCHEMICAL AND ESR SPECTRAL EVIDENCE FOR A STEREOSELECTIVE REARRANGEMENT OF RADICAL CATIONS DERIVED FROM AZOALKANES AND BICYCLOPENTANES [J].

ADAM, W ;

WALTER, H ;

CHEN, GF ;

WILLIAMS, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (08) :3007-3014

[3] WAGNER-MEERWEIN REARRANGEMENTS OF RADICAL CATIONS GENERATED BY TRIPHENYLPYRYLIUM TETRAFLUOROBORATE PHOTOSENSITIZED ELECTRON-TRANSFER OF AZOALKANES [J].

ADAM, W ;

DORR, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (05) :1570-1572

[4] DENITROGENATION OF BICYCLIC AZOALKANES THROUGH PHOTOSENSITIZED ELECTRON-TRANSFER - GENERATION AND INTRAMOLECULAR TRAPPING OF RADICAL CATIONS [J].

ADAM, W ;

SENDELBACH, J .

JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (20) :5316-5322

[5] REGIOSELECTIVE REARRANGEMENT OF BRIDGEHEAD-METHYL-SUBSTITUTED RADICAL CATIONS DERIVED FROM BICYCLO[2.1.0]PENTANES AND 2,3-DIAZABICYCLO[2.2.1]HEPT-2-ENES THROUGH PHOTOINDUCED ELECTRON-TRANSFER AND RADIOLYTIC OXIDATION - PRODUCT DISTRIBUTION AND MATRIX ESR STUDIES [J].

ADAM, W ;

SAHIN, C ;

SENDELBACH, J ;

WALTER, H ;

CHEN, GF ;

WILLIAMS, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (06) :2576-2584

[6] COMPARATIVE-STUDY OF THE PYROLYSIS, PHOTOINDUCED ELECTRON-TRANSFER (PET), AND LASER-JET AND 185-NM PHOTOCHEMISTRY OF ALKYL-SUBSTITUTED BICYCLIC AZOALKANES [J].

ADAM, W ;

DENNINGER, U ;

FINZEL, R ;

KITA, F ;

PLATSCH, H ;

WALTER, H ;

ZANG, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (13) :5027-5035

[7] PHOTOSENSITIZED ELECTRON-TRANSFER FROM AZOALKANES - GENERATION, FRAGMENTATION, AND REARRANGEMENT OF RADICAL CATIONS STRUCTURALLY RELATED TO DICYCLOPENTADIENE [J].

ADAM, W ;

SENDELBACH, J .

JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (20) :5310-5315

[8]

ADAM W, 1980, ANGEW CHEM-GER EDIT, V92, P815

[9] AZOALKANES AS ELECTRON-DONORS IN CHARGE-TRANSFER COMPLEXES - MOLECULAR-STRUCTURES WITH SACRIFICIAL (PI-STAR, SIGMA-STAR) AND INCREVALENT (V) ELECTRON-ACCEPTORS [J].

BLACKSTOCK, SC ;

KOCHI, JK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (08) :2484-2496

[10] REACTION OF AZOALKANES WITH ISOLABLE CATION RADICAL SALTS [J].

ENGEL, PS ;

ROBERTSON, DM ;

SCHOLZ, JN ;

SHINE, HJ .

JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (23) :6178-6187