THE CIEPLAK EFFECT - HYPERCONJUGATIVE INTERACTIONS IN DIELS-ALDER REACTIONS

被引：56

作者：

COXON, JM

MCDONALD, DQ

机构：

[1] Department of Chemistry, University of Canterbury, Christchurch

来源：

TETRAHEDRON LETTERS | 1992年 / 33卷 / 05期

关键词：

D O I：

10.1016/S0040-4039(00)92334-7

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Molecular orbital calculations of the transition states for the reactions of the dienes la-e with ethylene using the AM1 Hamiltonian show the diene C-X bond length for anti addition of the dienophile is longer than the comparable bond length when the X-substituent is syn to the approaching dienophile. The bond lengthening is consistent with hyperconjugative stabilization involving the donation of electron density from the sigma-bond of the anti substituent to the forming sigma*-orbital.

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页码：651 / 654

页数：4

相关论文

共 18 条

[1] ELECTRONIC FACTORS INFLUENCING THE ACTIVATION BARRIER OF THE DIELS-ALDER REACTION - AN ABINITIO STUDY [J].

BACH, RD ;

MCDOUALL, JJW ;

SCHLEGEL, HB ;

WOLBER, GJ .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (12) :2931-2935

[2] MC-SCF STUDY OF THE DIELS-ALDER REACTION BETWEEN ETHYLENE AND BUTADIENE [J].

BERNARDI, F ;

BOTTONI, A ;

FIELD, MJ ;

GUEST, MF ;

HILLIER, IH ;

ROBB, MA ;

VENTURINI, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (10) :3050-3055

[3] FURTHER EVIDENCE FOR THE ROLE OF D-PI-P-PI BONDING IN RHODIUM-MEDIATED HYDROBORATIONS [J].

BURGESS, K ;

VANDERDONK, WA ;

JARSTFER, MB ;

OHLMEYER, MJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (16) :6139-6144

[4] THE RHF-AM1 AND UHF-AM1 POTENTIAL-ENERGY SURFACES FOR THE DIELS-ALDER REACTION OF SUBSTITUTED BUTADIENES WITH SUBSTITUTED ETHENES .58. DETERMINATION OF REACTIVITY BY MO THEORY [J].

CHOI, JY ;

LEE, I .

JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1989, 85 :867-877

[5] HYPERCONJUGATION AS A FACTOR IN FACE SELECTIVITY DURING CYCLO-ADDITION [J].

CHUNG, WS ;

TURRO, NJ ;

SRIVASTAVA, S ;

LI, HF ;

LENOBLE, WJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (23) :7882-7883

[6] REVERSAL OF PI-FACIAL DIASTEREOSELECTION UPON ELECTRONEGATIVE SUBSTITUTION OF THE SUBSTRATE AND THE REAGENT [J].

CIEPLAK, AS ;

TAIT, BD ;

JOHNSON, CR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (22) :8447-8462

[7]

CIEPLAK AS, 1987, J AM CHEM SOC, V109, P5875

[8] FACIAL DIFFERENTIATION IN DIELS-ALDER REACTIONS TO DISSYMMETRIC CYCLOHEXA-1,3-DIENES [J].

COXON, JM ;

MACLAGAN, RGAR ;

MCDONALD, DQ ;

STEEL, PJ .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (07) :2542-2549

[9] MECHANISM OF THE DIELS-ALDER REACTION - REACTIONS OF BUTADIENE WITH ETHYLENE AND CYANOETHYLENES [J].

DEWAR, MJS ;

OLIVELLA, S ;

STEWART, JJP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (19) :5771-5779

[10] 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