Hyperconjugative effects in the stereoselective ring-opening reactions of oxetenoxides

被引：41

作者：

Mori, S ^{[1
]}

Shindo, M

机构：

[1] Ibaraki Univ, Fac Sci, Mito, Ibaraki 3108512, Japan

[2] Univ Tokushima, Inst Med Resources, Tokushima 7708505, Japan

来源：

ORGANIC LETTERS | 2004年 / 6卷 / 22期

关键词：

D O I：

10.1021/ol048499f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] Unexpectedly, the pattern of the stereoselectivity in the ring-opening reactions of lithium oxetenoxides is not consistent with the bulkiness of substituents, and both the bulkier tert-butyl and silyl substituents favor inward rotation. With the aid of B3LYP calculations, the hyperconjugative interaction between the breaking C-1-O sigma and its ant-periplanar Z-Me (Z = Si or C) sigma* orbital is found to be responsible among the secondary orbital interactions of the substituents and the oxetene moiety.

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页码：3945 / 3948

页数：4

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共 35 条

[1] Stereoelectronic effects and general trends in hyperconjugative acceptor ability of σ bonds [J].

Alabugin, IV ;

Zeidan, TA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (12) :3175-3185

[2] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[3] THE THERMAL RING-OPENING OF 3,3-DISUBSTITUTED CYCLOBUTENES [J].

CURRY, MJ ;

STEVENS, IDR .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1980, (10) :1391-1398

[4] Electronic control of stereoselectivities of electrocyclic reactions of cyclobutenes: A triumph of theory in the prediction of organic reactions [J].

Dolbier, WR ;

Koroniak, H ;

Houk, KN ;

Sheu, CM .

ACCOUNTS OF CHEMICAL RESEARCH, 1996, 29 (10) :471-477

[5] REMARKABLE, CONTRASTERIC, ELECTROCYCLIC RING-OPENING OF A CYCLOBUTENE [J].

DOLBIER, WR ;

KORONIAK, H ;

BURTON, DJ ;

BAILEY, AR ;

SHAW, GS ;

HANSEN, SW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (06) :1871-1872

[6]

GLENDENING ED, NBO VERSION 5 0 IMPL

[7]

HEHRE WJ, AB INTIIO MOL ORBITA

[8] Lewis acid promoted hetero [2+2] cycloaddition reactions of aldehydes with 10-propynyl-9(10H)-acridone.: A highly stereoselective synthesis of acrylic acid derivatives and 1,3-dienes using an electron deficient variant of ynamine [J].

Hsung, RP ;

Zificsak, CA ;

Wei, LL ;

Douglas, CJ ;

Xiong, H ;

Mulder, JA .

ORGANIC LETTERS, 1999, 1 (08) :1237-1240

[9] Geminal bond participation in the electrocyclic reactions: Torquoselectivities of silyl and trimethylsilyl derivatives of cyclobutene, iminocyclobutene, and cyclobutenone [J].

Ikeda, H ;

Kato, T ;

Inagaki, S .

CHEMISTRY LETTERS, 2001, (03) :270-271

[10] ELECTROCYCLIC RING OPENINGS OF DIALKYLCYCLOBUTENES - ANOMALIES EXPLAINED [J].

KALLEL, EA ;

YING, W ;

SPELLMEYER, DC ;

HOUK, KN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (19) :6759-6763

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