Estimation of the kinetic acidity from substrate conformation -: Stereochemical course of the deprotonation of cyclohexenyl carbamates

被引：19

作者：

Becker, Jochen ^{[1
]}

Grimme, Stefan ^{[1
]}

Froehlich, Roland ^{[1
]}

Hoppe, Dieter ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2007年 / 46卷 / 10期

关键词：

asymmetric synthesis; C-H acidity; carbanions; conformational analysis; density functional calculations;

D O I：

10.1002/anie.200603347

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Get the bends: The kinetic C-H acidity of cyclohex-2-enyl carbamates is dependent on the torsion angle between the α C-H bond and the π system of the adjacent double bond. A deprotonation study and DFT calculations of the activation energies for lithiation show that the ease of deprotonation is predictable from a conformational analysis of the substrates. Furthermore, the stereochemical course of substitution reactions was determined. (Chemical Equation Presented). © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：1645 / 1649

页数：5

共 57 条

[1]

Ahlbrecht H, 1999, SYNTHESIS-STUTTGART, P365

[2] ELECTRONIC-STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS - THE PROGRAM SYSTEM TURBOMOLE [J].

AHLRICHS, R ;

BAR, M ;

HASER, M ;

HORN, H ;

KOLMEL, C .

CHEMICAL PHYSICS LETTERS, 1989, 162 (03) :165-169

[3] An experimental and computational investigation of the enantioselective deprotonation of Boc-piperidine [J].

Bailey, WF ;

Beak, P ;

Kerrick, ST ;

Ma, SH ;

Wiberg, KB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (09) :1889-1896

[4] Metalation of 9-oxabicyclo[3.3.1]nonadiene -: the deprotonation path to bridgehead olefins [J].

Bassioni, Ghada ;

Koehler, Frank H. .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2006, 2006 (12) :2795-2802

[5] ALPHA-LITHIOAMINE SYNTHETIC EQUIVALENTS - SYNTHESES OF DIASTEREOISOMERS FROM THE BOC PIPERIDINES [J].

BEAK, P ;

LEE, WK .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (09) :2578-2580

[6] FORMATION, STRUCTURES, AND REACTIONS OF SELECTED ALPHA'-LITHIOALLYL AMIDES [J].

BEAK, P ;

LEE, B .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (02) :458-464

[7]

BECK P, 2003, TOP ORGANOMETAL CHEM, V6, P134

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

BECKE, AD .

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

[9] Stereoelectronic, torsional, and steric effects on rates of enolization of ketones [J].

Behnam, SM ;

Behnam, SE ;

Ando, K ;

Green, NS ;

Houk, KN .

JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (26) :8970-8978

[10] Outlier treatment in data merging [J].

Blessing, RH .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1997, 30 :421-426

← 1 2 3 4 5 6 →