STEREOCHEMISTRY OF BASE-PROMOTED 1,2-ELIMINATION FROM EXO-2-BICYCLO[2.2.1]HEPTYL TOSYLATE AND CHLORIDE

被引：6

作者：

BARTSCH, RA ^{[1
]}

LEE, JG ^{[1
]}

机构：

[1] PUSAN NATL UNIV,DEPT CHEM,PUSAN 609735,SOUTH KOREA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 01期

关键词：

D O I：

10.1021/jo00001a041

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Elimination reactions of exo-2-bicyclo[2.2.1]heptyl tosylate and chloride and their exo-3-deuterated analogues are studied in base-solvent systems that induce clean bimolecular 1,2-eliminations. The relative propensities for competitive syn-exo and anti-endo-H elimination modes are assessed from nonkinetically determined deuterium isotope effects and the deuterium content in the bicyclo[2.2.1]hept-2-ene formed from the deuterated substrates. The competition between syn-exo and anti-endo-H elimination is influenced by base association, which stabilizes the syn elimination transition state. Potential steric hindrance by oversized dissociated bases has no effect on the elimination stereochemistry.

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页码：212 / 217

页数：6

相关论文

共 21 条

[1] STEREOCHEMISTRY IN BETA ELIMINATIONS FROM EXO-2-NORBORNYL TOSYLATE - EFFECT OF BASE ASSOCIATION [J].

BARTSCH, RA ;

KAYSER, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (13) :4346-4347

[2] IONIC ASSOCIATION IN BASE-PROMOTED BETA-ELIMINATION REACTIONS [J].

BARTSCH, RA .

ACCOUNTS OF CHEMICAL RESEARCH, 1975, 8 (07) :239-245

[3] BASE-PROMOTED 1,2-ELIMINATIONS FROM ENDO-2-BICYCLO[2.2.1]HEPTYL HALIDES AND ARENESULFONATES [J].

BARTSCH, RA ;

LEE, JG .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (18) :5247-5252

[4] STEREOCHEMICAL AND BASE SPECIES DICHOTOMIES IN OLEFIN-FORMING E2 ELIMINATIONS [J].

BARTSCH, RA ;

ZAVADA, J .

CHEMICAL REVIEWS, 1980, 80 (06) :453-494

[5] STEREOCHEMISTRY OF BETA ELIMINATION IN 2-NORBORNYL AND 7,7-DIMETHYL-2-NORBORNYL TOSYLATES . EVIDENCE FOR PREFERENTIAL ATTACK BY BASE ON EXO-3-HYDROGEN IN BOTH SYSTEMS [J].

BROWN, HC ;

LIU, KT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1970, 92 (01) :200-&

[6] A REMARKABLE STEREOSELECTIVITY IN OXYMERCURATION-DEMERCURATION OF NORBORNENE 7.7-DIMETHYLNORNENE AND RELATED DERIVATIVES [J].

BROWN, HC ;

KAWAKAMI, JH ;

IKEGAMI, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1967, 89 (06) :1525-&

[7] SOLVOMERCURATION-DEMERCURATION .4. MONOHYDRATION OF REPRESENTATIVE DIENES VIA OXYMERCURATION-DEMERCURATION [J].

BROWN, HC ;

GEOGHEGA.PJ ;

LYNCH, GJ ;

KUREK, JT .

JOURNAL OF ORGANIC CHEMISTRY, 1972, 37 (12) :1941-&

[8] HYDROBORATION .9. HYDROBORATION OF CYCLIC AND BICYCLIC OLEFINS-STEREOCHEMISTRY OF HYDROBORATION REACTION [J].

BROWN, HC ;

ZWEIFEL, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1961, 83 (11) :2544-&

[9]

BROWN HC, 1962, HYDROBORATION, P130

[10] ELIMINATION REACTIONS .2. HOFMANN ELIMINATION IN BICYCLIC COMPOUNDS [J].

COKE, JL ;

COOKE, MP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1967, 89 (25) :6701-&