CONTROL OF REGIOSELECTIVITY IN THE DI-PI-METHANE REARRANGEMENT - TRIPLET-SENSITIZED PHOTOISOMERIZATION OF BENZONORBORNADIENES CARRYING CYANO SUBSTITUENTS IN THE ARYL AND VINYL SEGMENTS

被引：31

作者：

PAQUETTE, LA ^{[1
]}

KU, AY ^{[1
]}

SANTIAGO, C ^{[1
]}

ROZEBOOM, MD ^{[1
]}

HOUK, KN ^{[1
]}

机构：

[1] LOUISIANA STATE UNIV,DEPT CHEM,BATON ROUGE,LA 70803

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1979年 / 101卷 / 20期

关键词：

D O I：

10.1021/ja00514a017

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Triplet-sensitized irradiation of 2-cyanobenzonorbornadiene (10) gives rise exclusively to 3-cyanotetracyclo[5.4.0.02,4.03,6]undeca-l(7),8,10-triene (30). This strong preference for benzo-vinyl bridging to C3 has also been observed in the case of the four possible aryl-substituted dicyano derivatives. In all of these examples, striking regiospecificity is exhibited, despite untoward aryl polar effects in two examples. This bonding preference is shown to conform to the vacant orbital energies and shapes present in the starting benzonorbornadienes as calculated by STO-3G procedures and supported by photoelectron spectroscopy. The synthetic approaches to the polar substituted benzonorbornadienes are also detailed. © 1979, American Chemical Society. All rights reserved.

引用

收藏

页码：5972 / 5980

页数：9

相关论文

共 45 条

[11] PHOTOREARRANGEMENT OF BENZONORBORNADIENES [J].

EDMAN, JR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (14) :3454-&

[12] ORGANOMETALLIC COMPOUNDS OF GROUP-3 .33. POLAR AND STEREOCHEMICAL FACTORS IN CARBALUMINATION OF OLEFINS - ADDITION OF TRIPHENYLALUMINUM TO 6-SUBSTITUTED BENZONORBORNADIENES [J].

EISCH, JJ ;

BURLINSON, NE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (03) :753-761

[13] INTERACTION BETWEEN PARA DIMETHOXYBENZENE AND NORBORNYLENE IN 2 RIGID MODEL COMPOUNDS [J].

FILIPESCU, N ;

CHANG, DSC ;

BOTTOMLE.CG ;

BENSON, RE ;

JOSEY, AD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (17) :5990-+

[14] DI-PI-METHANE REARRANGEMENTS OF 1,4-DIHYDRO-1,4-METHANO-5,8-DIOLS AND 1,4-DIHYDRO-1-ETHANONAPHTHALENE-5,8-DIOLS [J].

FUERNISS, SJ ;

OLANDER, CR ;

WHEELER, DMS ;

MCPHAIL, AT ;

ONAN, KD .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1976, (05) :550-555

[15] RACEMIZATION IN SOLVOLYSIS OF EXO-2-BENZNORBORNENYL BROSYLATE [J].

GIDDINGS, WP ;

DIRLAM, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1963, 85 (23) :3900-&

[16] EFFECTS OF A NITRO SUBSTITUENT ON DI-PI-METHANE REARRANGEMENTS OF BENZONORBORNADIENE AND ITS [3.2.1] HOMOLOG [J].

HAHN, RC ;

JOHNSON, RP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (05) :1508-1513

[17]

Hine J., 1962, PHYSICAL ORGANIC CHE, P87

[18] DI-PI-METHANE AND OXA-DI-PI-METHANE REARRANGEMENTS [J].

HIXSON, SS ;

MARIANO, PS ;

ZIMMERMA.HE .

CHEMICAL REVIEWS, 1973, 73 (05) :531-551

[19] IONIZATION-POTENTIALS, ELECTRON AFFINITIES, AND REACTIVITIES OF CYANOALKENES AND RELATED ELECTRON-DEFICIENT ALKENES - FRONTIER MOLECULAR-ORBITAL TREATMENT OF CYANOALKENE REACTIVITIES IN CYCLOADDITION, ELECTROPHILIC, NUCLEOPHILIC, AND RADICAL REACTIONS [J].

HOUK, KN ;

MUNCHAUSEN, LL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (04) :937-946

[20] SCHIZOPHRENIC SUBSTITUENTS - ORIGIN OF ANOMALOUS SUBSTITUENT EFFECTS ON CYCLOADDITION REGIOSELECTIVITY [J].

HOUK, KN ;

DOMELSMITH, LN ;

STROZIER, RW ;

PATTERSON, RT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (20) :6531-6533

← 1 2 3 4 5 →