Haloboration of Internal Alkynes with Boronium and Borenium Cations as a Route to Tetrasubstituted Alkenes

被引：84

作者：

Lawson, James R. ^{[1
]}

Clark, Ewan R. ^{[1
]}

Cade, Ian A. ^{[1
]}

Solomon, Sophia A. ^{[1
]}

Ingleson, Michael J. ^{[1
]}

机构：

[1] Univ Manchester, Sch Chem, Manchester M13 9PL, Lancs, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2013年 / 52卷 / 29期

基金：

英国工程与自然科学研究理事会;

关键词：

borenium ions; boronate esters; haloboration; synthetic methods; tetrasubstituted alkenes; FRUSTRATED LEWIS PAIRS; CARBOBORATION; ELECTROPHILES; INTERMEDIATE; CHLOROBORANE; ACTIVATION; REACTIVITY; CHEMISTRY; INSERTION;

D O I：

10.1002/anie.201302609

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Hail boration! 2-Dimethylaminopyridine-ligated dihaloborocations [X 2B(2-DMAP)]+ with a strained four-membered boracycle were used for the haloboration of terminal and dialkyl internal alkynes (see scheme). Esterification then provided vinyl boronate esters as useful precursors to tetrasubstituted alkenes. Following mechanistic studies, the scope of the haloboration was expanded simply by variation of the amine. Pin=2,3-dimethyl-2, 3-butanedioxy. © 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of Creative Commons the Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

引用

页码：7518 / 7522

页数：5

共 51 条

[1] Copper(I)-Catalyzed Formal Carboboration of Alkynes: Synthesis of Tri- and Tetrasubstituted Vinylboronates [J].

Alfaro, Ricardo ;

Parra, Alejandro ;

Aleman, Jose ;

Garcia Ruano, Jose Luis ;

Tortosa, Mariola .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (37) :15165-15168

[2] Mechanistic Studies into Amine-Mediated Electrophilic Arene Borylation and Its Application in MIDA Boronate Synthesis [J].

Bagutski, Viktor ;

Del Grosso, Alessandro ;

Carrillo, Josue Ayuso ;

Cade, Ian A. ;

Helm, Matthew D. ;

Lawson, James R. ;

Singleton, Paul J. ;

Solomon, Sophia A. ;

Marcelli, Tommaso ;

Ingleson, Michael J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (01) :474-487

[3] Hydroborations catalysed by transition metal complexes [J].

Beletskaya, I ;

Pelter, A .

TETRAHEDRON, 1997, 53 (14) :4957-5026

[4]

Brown H.C., 1981, ALDRICHIM ACTA, V14, P3

[5] The Hydride-Ion Affinity of Borenium Cations and Their Propensity to Activate H2 in Frustrated Lewis Pairs [J].

Clark, Ewan R. ;

Del Grosso, Alessandro ;

Ingleson, Michael J. .

CHEMISTRY-A EUROPEAN JOURNAL, 2013, 19 (07) :2462-2466

[6] Palladium-catalyzed carboboration of alkynes using chloroborane and organozirconium reagents [J].

Daini, Masaki ;

Suginome, Michinori .

CHEMICAL COMMUNICATIONS, 2008, (41) :5224-5226

[7] Palladium-catalyzed trans- and cis-carboboration of Alkynes tethered to chloroborane with organozirconium reagents:: Ligand-dependent complementary stereoselectivity [J].

Daini, Masaki ;

Yamamoto, Akihiko ;

Suginome, Michinori .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (10) :2918-2919

[8] Cationic Tricoordinate Boron Intermediates: Borenium Chemistry from the Organic Perspective [J].

De Vries, Timothy S. ;

Prokofjevs, Aleksandrs ;

Vedejs, Edwin .

CHEMICAL REVIEWS, 2012, 112 (07) :4246-4282

[9] Simple inexpensive boron electrophiles for direct arene borylation [J].

Del Grosso, Alessandro ;

Helm, Matthew D. ;

Solomon, Sophia A. ;

Caras-Quintero, Dolores ;

Ingleson, Michael J. .

CHEMICAL COMMUNICATIONS, 2011, 47 (46) :12459-12461

[10] Terminal Alkyne Activation by Frustrated and Classical Lewis Acid/Phosphine Pairs [J].

Dureen, Meghan A. ;

Stephan, Douglas W. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (24) :8396-+

← 1 2 3 4 5 6 →