SOLVENT EFFECTS ON ENDO/EXO-SELECTIVITIES AND REGIO-SELECTIVITIES OF DIELS-ALDER REACTIONS OF CARBONYL-CONTAINING DIENOPHILES

被引：43

作者：

CATIVIELA, C ^{[1
]}

GARCIA, JI ^{[1
]}

MAYORAL, JA ^{[1
]}

SALVATELLA, L ^{[1
]}

机构：

[1] UNIV ZARAGOZA,CSIC,INST CIENCIA MAT ARAGON,DEPT QUIM ORGAN,E-50009 ZARAGOZA,SPAIN

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1994年 / 04期

关键词：

D O I：

10.1039/p29940000847

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The selectivity of Diels-Alder reactions of methyl vinyl ketone and methyl acrylate, with cyclopentadiene and isoprene, have been studied in 18 pure solvents and aqueous mixtures. The results obtained have been analysed by means of regression models, using empirical solvent parameters. The endo/exo selectivity mainly depends on the solvophobic (S-p) and hydrogen bond donor (alpha) properties of the solvent. The influence of the dipolarity (pi*) is only observed in the reactions with methyl acrylate. Regioselectivity almost exclusively depends on the hydrogen bond donor ability of the solvent. The double coordination observed with highly hydrogen bond donating solvents in the case of methyl vinyl ketone greatly increases the para/meta isomer ratio.

引用

页码：847 / 851

页数：5

共 29 条

[1] ABRAHAM MH, 1989, J CHEM SOC P2, P339
[2] ABRAHAM MH, COMMUNICATION
[3] CORRELATION OF SOLVENT EFFECTS ON STEREOSELECTIVITIES OF DIELS-ALDER REACTIONS BY MEANS OF LINEAR FREE ENERGY RELATIONSHIPS - A NEW EMPIRICAL MEASURE OF SOLVENT POLARITY
BERSON, JA
MUELLER, WA
HAMLET, Z
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1962, 84 (02) : 297 - &
[4] SOLVENT EFFECTS ON A DIELS-ALDER REACTION FROM COMPUTER-SIMULATIONS
BLAKE, JF
JORGENSEN, WL
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (19) : 7430 - 7432
[5] CORRELATIONS OF RATE AND SELECTIVITY OF A DIELS-ALDER REACTION WITH SP PARAMETERS
CATIVIELA, C
MAYORAL, JA
AVENOZA, A
PEREGRINA, JM
ROY, MA
[J]. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1990, 3 (06) : 414 - 418
[6] EXPERIMENTAL AND THEORETICAL-STUDY OF THE INFLUENCE OF THE SOLVENT ON ASYMMETRIC DIELS-ALDER REACTIONS
CATIVIELA, C
GARCIA, JI
MAYORAL, JA
ROYO, AJ
SALVATELLA, L
ASSFELD, X
RUIZLOPEZ, MF
[J]. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1992, 5 (05) : 230 - 238
[7] FLUORINATED ALCOHOLS AS SOLVENTS FOR DIELS-ALDER REACTIONS OF CHIRAL ACRYLATES
CATIVIELA, C
GARCIA, JI
MAYORAL, JA
ROYO, AJ
SALVATELLA, L
[J]. TETRAHEDRON-ASYMMETRY, 1993, 4 (07) : 1613 - 1618
[8] DEVELOPMENT OF A MODEL TO EXPLAIN THE INFLUENCE OF THE SOLVENT ON THE RATE AND SELECTIVITY OF DIELS-ALDER REACTIONS
CATIVIELA, C
GARCIA, JI
MAYORAL, JA
AVENOZA, A
PEREGRINA, JM
ROY, MA
[J]. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1991, 4 (01) : 48 - 52
[9] CATIVIELA C, IN PRESS CAN J CHEM
[10] CORSICOCODA A, 1989, TETRAHEDRON, V45, P775

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