Combined quantum chemical and MM-approach to the endo/exo selectivity of Diels-Alder reactions in polar media

被引：7

作者：

Schlachter, I

Mattay, J

Suer, J

Howeler, U

Wurthwein, G

Wurthwein, EU

机构：

[1] UNIV MUNSTER,INST ORGAN CHEM,D-48149 MUNSTER,GERMANY

[2] CHRISTIAN ALBRECHTS UNIV KIEL,INST ORGAN CHEM,D-24098 KIEL,GERMANY

来源：

TETRAHEDRON | 1997年 / 53卷 / 01期

关键词：

D O I：

10.1016/S0040-4020(96)00957-X

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The endolexo selectivity of Diels-alder reactions in water and methanol is studied with semiempirical methods using the SCRF approach and a combined quantum chemical (transition state) and molecular mechanics (solvent molecules) method (QC/MM) to determine the effect of protic solvents on the transition slate energies. Evidently, the number of hydrogen bonds that causes strong Coulomb interaction, discriminates heals of formation of transition stales. The results indicate that the s-cis/s-trans conformation of acrylates controls the endolexo selectivity. Copyright (C) 1996 Elsevier Science Ltd

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页码：119 / 132

页数：14

相关论文

共 40 条

[1]

BERNARDI F, 1995, AIP C P, V330, P145

[2] CORRELATION OF SOLVENT EFFECTS ON STEREOSELECTIVITIES OF DIELS-ALDER REACTIONS BY MEANS OF LINEAR FREE ENERGY RELATIONSHIPS - A NEW EMPIRICAL MEASURE OF SOLVENT POLARITY [J].

BERSON, JA ;

MUELLER, WA ;

HAMLET, Z .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1962, 84 (02) :297-&

[3] SOLVENT EFFECTS ON A DIELS-ALDER REACTION FROM COMPUTER-SIMULATIONS [J].

BLAKE, JF ;

JORGENSEN, WL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (19) :7430-7432

[4] MECHANISM AND SITE SELECTIVITY IN THE DIELS-ALDER REACTION BETWEEN PROTOANEMONIN AND BUTADIENE - A THEORETICAL-STUDY [J].

BRANCHADELL, V ;

ORTI, J ;

ORTUNO, RM ;

OLIVA, A ;

FONT, J ;

BERTRAN, J ;

DANNENBERG, JJ .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (06) :2190-2193

[5] SELECTIVE DIELS-ALDER REACTIONS IN AQUEOUS-SOLUTIONS AND SUSPENSIONS [J].

BRESLOW, R ;

MAITRA, U ;

RIDEOUT, D .

TETRAHEDRON LETTERS, 1983, 24 (18) :1901-1904

[6]

CARMONA P, 1982, J AM CHEM SOC, V104, P177

[7] EXPERIMENTAL AND THEORETICAL-STUDY OF THE INFLUENCE OF THE SOLVENT ON ASYMMETRIC DIELS-ALDER REACTIONS [J].

CATIVIELA, C ;

GARCIA, JI ;

MAYORAL, JA ;

ROYO, AJ ;

SALVATELLA, L ;

ASSFELD, X ;

RUIZLOPEZ, MF .

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1992, 5 (05) :230-238

[8] THEORETICAL-STUDIES OF HYDROGEN-BONDED COMPLEXES USING SEMIEMPIRICAL METHODS [J].

COITINO, EL ;

IRVING, K ;

RAMA, J ;

IGLESIAS, A ;

PAULINO, M ;

VENTURA, ON .

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 1990, 69 :405-426

[9] THE DEVELOPMENT AND USE OF QUANTUM-MECHANICAL MOLECULAR-MODELS .76. AM1 - A NEW GENERAL-PURPOSE QUANTUM-MECHANICAL MOLECULAR-MODEL [J].

DEWAR, MJS ;

ZOEBISCH, EG ;

HEALY, EF ;

STEWART, JJP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (13) :3902-3909

[10] A COMBINED QUANTUM-MECHANICAL AND MOLECULAR MECHANICAL POTENTIAL FOR MOLECULAR-DYNAMICS SIMULATIONS [J].

FIELD, MJ ;

BASH, PA ;

KARPLUS, M .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1990, 11 (06) :700-733

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