FREE-ENERGY PROFILE FOR A HOST-ACCELERATED DIELS-ALDER REACTION - THE SOURCES OF EXO SELECTIVITY

被引:56
作者
WALTER, CJ [1 ]
SANDERS, JKM [1 ]
机构
[1] UNIV CAMBRIDGE,CHEM LAB,CAMBRIDGE CTR MOLEC RECOGNIT,CAMBRIDGE CB2 1EW,ENGLAND
来源
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH | 1995年 / 34卷 / 02期
关键词
DIELS-ALDER REACTIONS; ENZYME MODELS; HOST-GUEST CHEMISTRY; KINETICS; PORPHYRINOIDS;
D O I
10.1002/anie.199502171
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Simultaneous reduction of the activation energy for the exo reaction and increase of that for the endo reaction explain how a cyclic porphyrin trimer that can bind diene 1 and dienophile 2 in its cavity increases the exo selectivity of a Diels–Alder reaction and accelerates it dramatically. (Figure Presented.) Copyright © 1995 by VCH Verlagsgesellschaft mbH, Germany
引用
收藏
页码:217 / 219
页数:3
相关论文
共 20 条
[1]   FREE-ENERGY PROFILE FOR REACTION CATALYZED BY TRIOSEPHOSPHATE ISOMERASE [J].
ALBERY, WJ ;
KNOWLES, JR .
BIOCHEMISTRY, 1976, 15 (25) :5627-5631
[2]   SYNTHESIS OF A CYCLIC PORPHYRIN TRIMER WITH A SEMI-RIGID CAVITY [J].
ANDERSON, HL ;
SANDERS, JKM .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (22) :1714-1715
[3]   EXPANDING ROLES FOR TEMPLATES IN SYNTHESIS [J].
ANDERSON, S ;
ANDERSON, HL ;
SANDERS, JKM .
ACCOUNTS OF CHEMICAL RESEARCH, 1993, 26 (09) :469-475
[4]   USE OF BINDING-ENERGY IN CATALYSIS - OPTIMIZATION OF RATE IN A MULTISTEP REACTION [J].
AVIS, JM ;
FERSHT, AR .
BIOCHEMISTRY, 1993, 32 (20) :5321-5326
[5]   TOWARDS SYNTHETIC ENZYMES BASED ON PORPHYRINS AND STEROIDS [J].
BONARLAW, RP ;
MACKAY, LG ;
WALTER, CJ ;
MARVAUD, V ;
SANDERS, JKM .
PURE AND APPLIED CHEMISTRY, 1994, 66 (04) :803-810
[6]   AN ANTIBODY-CATALYZED BIMOLECULAR DIELS-ALDER REACTION [J].
BRAISTED, AC ;
SCHULTZ, PG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (20) :7430-7431
[7]   CATALYTIC CYCLOPHANES .4. SUPRAMOLECULAR CATALYSIS OF BENZOIN CONDENSATIONS BY A THIAZOLIUM CYCLOPHANE [J].
DIEDERICH, F ;
LUTTER, HD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (22) :8438-8446
[8]  
Fringuelli F., 1990, DIENES DIELSALDER RE
[9]   CONTROL OF THE EXO-PATHWAY AND ENDO-PATHWAY OF THE DIELS-ALDER REACTION BY ANTIBODY CATALYSIS [J].
GOUVERNEUR, VE ;
HOUK, KN ;
DEPASCUALTERESA, B ;
BENO, B ;
JANDA, KD ;
LERNER, RA .
SCIENCE, 1993, 262 (5131) :204-208
[10]   ANTIBODY CATALYSIS OF A DIELS-ALDER REACTION [J].
HILVERT, D ;
HILL, KW ;
NARED, KD ;
AUDITOR, MTM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (26) :9261-9262