C-F Activation of Fluorobenzene by Silylium Carboranes: Evidence for Incipient Phenyl Cation Reactivity

被引：79

作者：

Duttwyler, Simon ^{[2
]}

Douvris, Christos ^{[3
]}

Fackler, Nathanael L. P. ^{[4
]}

Tham, Fook S. ^{[2
]}

Reed, Christopher A. ^{[1
]}

Baldridge, Kim K. ^{[2
]}

Siegel, Jay S. ^{[2
]}

机构：

[1] Univ Calif Riverside, Dept Chem, Ctr S&P Block Chem, Riverside, CA 92521 USA

[2] Univ Zurich, Inst Organ Chem, CH-8057 Zurich, Switzerland

[3] Univ Colorado, Dept Chem, Boulder, CO 80309 USA

[4] Nebraska Wesleyan Univ, Dept Chem, Lincoln, NE USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2010年 / 49卷 / 41期

基金：

美国国家科学基金会; 瑞士国家科学基金会;

关键词：

carboranes; C-F activation; fluorides; fluorobenzene; silyl cations; ARYL CATIONS; AB-INITIO; IONS; SOLVOLYSIS; GENERATION; SALTS; HYDRODEFLUORINATION; DEDIAZONIATION; SINGLET; BONDS;

D O I：

10.1002/anie.201003762

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Si(mply) rips it apart: C-F activation of fluorobenzene has been achieved using the extremely strong silyl Lewis acids [Et3Si(X)]+ (X=PhF or Et3SiH) and [(2,6-dixylyl-C6H 3)SiMe2] + paired with the anion CHB 11Cl11-. They abstract fluoride from unactivated fluorobenzene to give arylated products, consistent with phenyl-cation-like reactivity (see scheme). © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：7519 / 7522

页数：4

共 54 条

[51]

2-5

[52] Ab initio study of the SN1Ar and SN2Ar reactions of benzenediazonium ion with water. on the conception of "unimolecular dediazoniation" in solvolysis reactions [J].

Wu, ZY ;

Glaser, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (34) :10632-10639

[53] Catalytic C-F bond activation of nonactivated monofluoroarenes [J].

Young, RJ ;

Grushin, VV .

ORGANOMETALLICS, 1999, 18 (03) :294-296

[54]

Zollinger H., 1995, DIAZO CHEM

← 1 2 3 4 5 6 →