Unsymmetrical 1,1-diborated multisubstituted sp3-carbons formed via a metal-free concerted-asynchronous mechanism

被引：64

作者：

Cuenca, Ana B. ^{[1
]}

Cid, Jessica ^{[1
]}

Garcia-Lopez, Diego ^{[1
]}

Carbo, Jorge J. ^{[1
]}

Fernandez, Elena ^{[1
]}

机构：

[1] Univ Rovira & Virgili, Dept Quim Fis & Inorgan, E-43007 Tarragona, Spain

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2015年 / 13卷 / 37期

关键词：

GEM-DIMETALLIC COMPOUNDS; TERTIARY BORONIC ESTERS; ASYMMETRIC-SYNTHESIS; HYDROBORATION; DIBORYLATION; INSERTION; DIBORYLMETHANE; CONSTRUCTION; DERIVATIVES; CYCLOPROPYL;

D O I：

10.1039/c5ob01523e

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We have experimentally proved the unsymmetrical 1,1-diboration of diazo compounds, formed in situ from aldehydes and cyclic and non-cyclic ketones, in the absence of any transition metal complex. The heterolytic cleavage of the mixed diboron reagent, Bpin-Bdan, and the formation of two geminal C-Bpin and C-Bdan bonds has been rationalised based on DFT calculations to occur via a concerted-asynchronous mechanism. Diastereoselection is attained on substituted cyclohexanones and DFT studies provide understanding on the origin of the selectivity. The alkoxide-assisted selective deborylation of Bpin from multisubstituted sp(3)-carbon and generation of a Bdan stabilized carbanion, easily conducts a selective protodeboronation sequence.

引用

页码：9659 / 9664

页数：6

共 33 条

[1] Novel C1-bridged bisboronate derivatives by insertion of diazoalkanes into bis(pinacolato)diborane(4) [J].

Abu Ali, H ;

Goldberg, I ;

Kaufmann, D ;

Burmeister, C ;

Srebnik, M .

ORGANOMETALLICS, 2002, 21 (09) :1870-1876

[2] Addition reactions of bis(pinacolato)diborane(4) to carbonyl enones and synthesis of (pinacolato)2BCH2B and (pinacolato)2BCH2CH2B by insertion and coupling [J].

Abu Ali, H ;

Goldberg, I ;

Srebnik, M .

ORGANOMETALLICS, 2001, 20 (18) :3962-3965

[3] DARSTELLUNG UND EIGENSCHAFTEN VON CYCLOPROPYL-BORANEN [J].

BINGER, P ;

KOSTER, R .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1962, 74 (16) :652-&

[4] HYDROBORATION .50. HYDROBORATION OF REPRESENTATIVE ALKYNES WITH 9-BORABICYCLO[3.3.1]NONANE - SIMPLE SYNTHESIS OF VERSATILE VINYL BORA AND GEM-DIBORA INTERMEDIATES [J].

BROWN, HC ;

SCOUTEN, CG ;

LIOTTA, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (01) :96-99

[5] ORGANOBORANES .9. STRUCTURE OF ORGANOBORANES FORMED IN REACTION OF 1,3-BUTADIENE AND DIBORANE IN STOICHIOMETRIC RATIO - AN UNUSUAL THERMAL ISOMERIZATION OF THESE ORGANOBORANES [J].

BROWN, HC ;

NEGISHI, EI ;

GUPTA, SK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1970, 92 (08) :2460-+

[6] SYNTHESIS OF B-CYCLOPROPYL- AND B-CYCLOBUTYLBICYCLO[3.3.1]NONANE VIA RING CLOSURE OF BORON INTERMEDIATES . A CONVENIENT ENTRY INTO CYCLOPROPYL AND CYCLOBUTYL DERIVATIVES VIA HYDROBORATION [J].

BROWN, HC ;

RHODES, SP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (15) :4306-&

[7] HYDROBORATION .11. HYDROBORATION OF ACETYLENES - A CONVENIENT CONVERSION OF INTERNAL ACETYLENES INTO CIS-OLEFINS AND OF TERMINAL ACETYLENES INTO ALDEHYDES [J].

BROWN, HC ;

ZWEIFEL, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1961, 83 (18) :3834-&

[8]

CAINELLI G, 1965, TETRAHEDRON LETT, P3429

[9] Iridium-catalyzed diborylation of benzylic C-H bonds directed by a hydrosilyl group: synthesis of 1,1-benzyldiboronate esters [J].

Cho, Seung Hwan ;

Hartwig, John F. .

CHEMICAL SCIENCE, 2014, 5 (02) :694-698

[10] A Clear- Cut Example of Selective Bpin - Bdan Activation and Precise Bdan Transfer on Boron Conjugate Addition [J].

Cid, Jessica ;

Carbo, Jorge J. ;

Fernandez, Elena .

CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (13) :3616-3620

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