Catalytic Generation of Borenium Ions by Cooperative B-H Bond Activation: The Elusive Direct Electrophilic Borylation of Nitrogen Heterocycles with Pinacolborane

被引：155

作者：

Stahl, Timo ^{[1
]}

Muether, Kristine ^{[1
,2
,3
]}

Ohki, Yasuhiro ^{[2
,3
]}

Tatsumi, Kazuyuki ^{[2
,3
]}

Oestreich, Martin ^{[1
]}

机构：

[1] Tech Univ Berlin, Inst Chem, D-10623 Berlin, Germany

[2] Nagoya Univ, Grad Sch Sci, Dept Chem, Chikusa Ku, Nagoya, Aichi 4648602, Japan

[3] Nagoya Univ, Grad Sch Sci, Res Ctr Mat Sci, Chikusa Ku, Nagoya, Aichi 4648602, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 30期

关键词：

LEWIS-ACID; COMPLEXES; REACTIVITY; CHEMISTRY; ANILINES; BORINIUM; CATIONS;

D O I：

10.1021/ja405925w

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The B-H bond of typical boranes is heterolytically split by the polar Ru-S bond of a tethered ruthenium(II) thiolate complex, affording a ruthenium(II) hydride and borenium ions with a dative interaction with the sulfur atom. These stable adducts were spectroscopically characterized, and in one case, the B-H bond activation step was crystallographically verified, a snapshot of the sigma-bond metathesis. The borenium ions derived from 9-borabicyclo[3.3.1]nonane dimer [(9-BBN)(2)], pinacolborane (pinBH), and catecholborane (catBH) allowed for electrophilic aromatic substitution of indoles. The unprecedented electrophilic borylation with the pinB cation was further elaborated for various nitrogen heterocycles.

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页码：10978 / 10981

页数：4

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