The origin of the halogen effect on reactivity and reversibility of Diels-Alder cycloadditions involving furan

被引：95

作者：

Pieniazek, SN ^{[1
]}

Houk, KN ^{[1
]}

机构：

[1] Univ Calif Los Angeles, Dept Biochem & Chem, Los Angeles, CA 90095 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2006年 / 45卷 / 09期

关键词：

computer chemistry; cycloaddition; halogenation; oxygen heterocycles; retro reactions;

D O I：

10.1002/anie.200502677

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Origin and generality of the halogen effect in Diels-Alder reactions were explored with high-accuracy CBS-QB3 computations. Halogen substitution increases cycloaddition exergonicities and decreases activation barriers. This effect is attributed to the energetic preference for electronegative halogen substituents to be attached to a more highly alkylated, and therefore more electropositive, carbon framework. (Chemical Equation Presented). © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：1442 / 1445

页数：4

共 52 条

[21]

Kappe CO, 1997, TETRAHEDRON, V53, P14179

[22] TOTAL SYNTHESIS OF (+/-)-DIMETHYL JACONATE [J].

KLEIN, LL ;

SHANKLIN, MS .

JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (22) :5202-5209

[23] TOTAL SYNTHESIS OF (+/-)-NEMORENSIC ACID [J].

KLEIN, LL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (08) :2573-2574

[24] STRUCTURAL EFFECTS ON INTRAMOLECULAR FURAN CYCLO-ADDITIONS [J].

KLEIN, LL .

JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (10) :1770-1773

[25] STUDIES IN THE FURAN SERIES .23. PREPARATION OF SOME NEW 5-SUBSTITUTED FURFURYLALLYLARYLAMINES - INFLUENCE OF SUBSTITUENTS ON THE INTRAMOLECULAR DIELS-ALDER (IMDA) REACTION [J].

KLEPO, Z ;

JAKOPCIC, K .

JOURNAL OF HETEROCYCLIC CHEMISTRY, 1987, 24 (06) :1787-1791

[26] REVERSE DIELS-ALDER OR RETRODIENE REACTION [J].

KWART, H ;

KING, K .

CHEMICAL REVIEWS, 1968, 68 (04) :415-+

[27] 5-MEMBERED HETEROAROMATIC RINGS AS INTERMEDIATES IN ORGANIC-SYNTHESIS [J].

LIPSHUTZ, BH .

CHEMICAL REVIEWS, 1986, 86 (05) :795-819

[28] SYNTHESIS OF A FULLY UNSATURATED MOLECULAR BOARD [J].

LOFFLER, M ;

SCHLUTER, AD ;

GESSLER, K ;

SAENGER, W ;

TOUSSAINT, JM ;

BREDAS, JL .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1994, 33 (21) :2209-2212

[29]

LOFFLER M, 1994, ANGEW CHEM, V106, P2281

[30] NEW ELECTRONEGATIVITY SCALE FOR THE CORRELATION OF HEATS OF FORMATION .1. ALKYL DERIVATIVES [J].

LUO, YR ;

BENSON, SW .

JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (18) :5255-5257

← 1 2 3 4 5 6 →