Synthesis of Perfluoroalkyl-Substituted Vinylcyclopropanes by Way of Enhanced Neighboring Group Participation

被引：18

作者：

Kelly, Christopher B. ^{[1
]}

Mercadante, Michael A. ^{[1
]}

Carnaghan, Emma R. ^{[1
]}

Doherty, Matthew J. ^{[2
]}

Fager, Diana C. ^{[2
]}

Hauck, John J. ^{[2
]}

MacInnis, Allyson E. ^{[2
]}

Tilley, Leon J. ^{[2
]}

Leadbeater, Nicholas E. ^{[1
,3
]}

机构：

[1] Univ Connecticut, Dept Chem, Storrs, CT 06269 USA

[2] Stonehill Coll, Dept Chem, Easton, MA 02357 USA

[3] Univ Connecticut, Ctr Hlth, Dept Community Med & Hlth Care, Exchange, Farmington, CT 06030 USA

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2015年 / 2015卷 / 19期

基金：

美国国家科学基金会;

关键词：

Synthetic methods; Fluorine; Organofluorine compounds; Organosilicon compounds; Cyclopropanes; Carbocations; FLUORINE; SOLVOLYSIS; C4H7+; IONS; CYCLOPROPYLCARBINYL; GENERATION; ENERGIES; CATION; MODES;

D O I：

10.1002/ejoc.201500565

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A simple, high yielding, two-step, one-pot protocol for the preparation of trifluoromethyl-substituted vinylcyclopropanes from -CF3 homoallyl alcohols is disclosed. Destabilization of the cationic intermediate by the electron-withdrawing CF3 group greatly enhances neighboring group participation of the alkene, allowing ring closure to predominate. The reaction can be extended to the difluoromethyl and pentafluoroethyl group, enabling the preparation of a diverse array of fluoroalkyl-substituted vinylcyclopropanes.

引用

页码：4071 / 4076

页数：6

共 48 条

[1] Metabolically Stable tert-Butyl Replacement [J].

Barnes-Seeman, David ;

Jain, Monish ;

Bell, Leslie ;

Ferreira, Suzie ;

Cohen, Scott ;

Chen, Xiao-Hui ;

Amin, Jakal ;

Snodgrass, Brad ;

Hatsis, Panos .

ACS MEDICINAL CHEMISTRY LETTERS, 2013, 4 (06) :514-516

[2] STEREOCHEMICAL COURSE OF SOLVOLYTIC 1,3-DEOXYSILYLATION [J].

COOPE, J ;

SHINER, VJ .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (18) :4270-4271

[3] SOLVOLYTIC ACCELERATION ACCOMPANYING (TRIMETHYLSILYL)METHYL MIGRATION [J].

COOPE, J ;

SHINER, VJ ;

ENSINGER, MW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (07) :2834-2835

[4] Homoallyl-cyclopropylcarbinyl cation manifold. Trimethylsilyl versus aryl stabilization [J].

Creary, Xavier ;

O'Donnell, Benjamin D. ;

Vervaeke, Marie .

JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (09) :3360-3368

[5] A FACILE SYNTHESIS OF METHANESULFONATE ESTERS [J].

CROSSLAN.RK ;

SERVIS, KL .

JOURNAL OF ORGANIC CHEMISTRY, 1970, 35 (09) :3195-&

[6] GAMMA-SILICON STABILIZATION OF CARBONIUM-IONS [J].

DAVIDSON, ER ;

SHINER, VJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (11) :3135-3137

[7] Synthesis of cyclopropane containing natural products [J].

Donaldson, WA .

TETRAHEDRON, 2001, 57 (41) :8589-8627

[8] Synthesis of trans-2-(Trifluoromethyl)cyclopropanes via Suzuki Reactions with an N-Methyliminodiacetic Acid Boronate [J].

Duncton, Matthew A. J. ;

Singh, Rajinder .

ORGANIC LETTERS, 2013, 15 (17) :4284-4287

[9]

Fairhurst R.A., 2011, PCT Int. Appl, Patent No. 2011000905

[10]

Faust R, 2001, ANGEW CHEM INT EDIT, V40, P2251, DOI 10.1002/1521-3773(20010618)40:12<2251::AID-ANIE2251>3.0.CO

← 1 2 3 4 5 →