1,3-γ-Silyl-elimination in electron-deficient cationic systems

被引：22

作者：

Mercadante, Michael A. ^{[2
]}

Kelly, Christopher B. ^{[2
]}

Hamlin, Trevor A. ^{[2
]}

Delle Chiaie, Kayla R. ^{[1
]}

Drago, Michael D. ^{[1
]}

Duffy, Katherine K. ^{[1
]}

Dumas, Megan T. ^{[1
]}

Fager, Diana C. ^{[1
]}

Glod, Bryanna L. C. ^{[1
]}

Hansen, Katherine E. ^{[1
]}

Hill, Cameron R. ^{[1
]}

Leising, Rebecca M. ^{[1
]}

Lynes, Catherine L. ^{[1
]}

MacInnis, Allyson E. ^{[1
]}

McGohey, Madeline R. ^{[1
]}

Murray, Stephanie A. ^{[1
]}

Piquette, Marc C. ^{[1
]}

Roy, Shaina L. ^{[1
]}

Smith, Ryan M. ^{[1
]}

Sullivan, Katherine R. ^{[1
]}

Truong, Bao H. ^{[1
]}

Vailonis, Kristina M. ^{[1
]}

Gorbatyuk, Vitaliy ^{[2
]}

Leadbeater, Nicholas E. ^{[2
,3
]}

Tilley, Leon J. ^{[1
]}

机构：

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

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

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

来源：

CHEMICAL SCIENCE | 2014年 / 5卷 / 10期

基金：

美国国家科学基金会;

关键词：

NEIGHBORING-GROUP PARTICIPATION; GAMMA-SILICON STABILIZATION; MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; TRIFLUOROMETHYL GROUP; CARBONIUM-IONS; STEREOSELECTIVE-SYNTHESIS; CYCLOPROPANE FORMATION; MEDICINAL CHEMISTRY; HARTREE-FOCK;

D O I：

10.1039/c4sc01732c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Placement of an electron-withdrawing trifluoromethyl group (-CF3) at a putative cationic centre enhances gamma-silyl neighbouring-group participation (NGP). In stark contrast to previously studied gamma-silyl-substituted systems, the preferred reaction pathway is 1,3-gamma-silyl elimination, giving ring closure over solvent substitution or alkene formation. The scope of this cyclopropanation reaction is explored for numerous cyclic and acyclic examples, proving this method to be a viable approach to preparing CF3-substituted cyclopropanes and bicyclic systems, both containing quaternary centres. Rate-constants, kinetic isotope effects, and quantum mechanical calculations provided evidence for this enhancement and further elaborated the disparity in the reaction outcome between these systems and previously studied gamma-silyl systems.

引用

页码：3983 / 3994

页数：12

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