A Highly Active Phosphine-Borane Organocatalyst for the Reduction of CO2 to Methanol Using Hydroboranes

被引：276

作者：

Courtemanche, Marc-Andre ^{[1
]}

Legare, Marc-Andre ^{[1
]}

Maron, Laurent ^{[2
]}

Fontaine, Frederic-Georges ^{[1
]}

机构：

[1] Univ Laval, Dept Chim, Ctr Catalyse & Chim Verte C3V, Quebec City, PQ G1V 0A6, Canada

[2] Univ Toulouse, CNRS, UPS, INSA,LCPNO,UMR 5215, Toulouse, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 25期

基金：

加拿大自然科学与工程研究理事会;

关键词：

FRUSTRATED LEWIS PAIRS; CARBON-DIOXIDE; HOMOGENEOUS HYDROGENATION; CATALYST; HYDROSILYLATION; FIXATION; CONVERSION;

D O I：

10.1021/ja404585p

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In this work, we report that organocatalyst 1-Bcat-2-PPh2-C6H4 ((1); cat = catechol) acts as an ambiphilic metal-free system for the reduction of carbon dioxide in presence of hydroboranes (HBR2 = HBcat (catecholborane), HBpin (pinacolborane), 9-BBN (9-borabicyclo[3.3.1]nonane), BH3 center dot SMe2 and BH3 center dot THF) to generate CH3OBR2 or (CH3OBO)(3), products that can be readily hydrolyzed to methanol. The yields can be as high as 99% with exclusive formation of CH3OBR2 or (CH3OBO)(3) with TON (turnover numbers) and TOF (turnover frequencies) reaching >2950 and 853 h(-1), respectively. Furthermore, the catalyst exhibits "living" behavior: once the first loading is consumed, it resumes its activity on adding another loading of reagents.

引用

页码：9326 / 9329

页数：4

共 39 条

[1]

[Anonymous], J CHEM SOC REV, DOI DOI 10.1039/C0CS00129E

[2] Geminal Phosphorus/Aluminum-Based Frustrated Lewis Pairs: C-H versus C≡C Activation and CO2 Fixation [J].

Appelt, Christian ;

Westenberg, Hauke ;

Bertini, Federica ;

Ehlers, Andreas W. ;

Slootweg, J. Chris ;

Lammertsma, Koop ;

Uhl, Werner .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (17) :3925-3928

[3] Utilisation of CO2 as a chemical feedstock:: opportunities and challenges [J].

Aresta, Michele ;

Dibenedetto, Angela .

DALTON TRANSACTIONS, 2007, (28) :2975-2992

[4] Non-Metal-Mediated Homogeneous Hydrogenation of CO2 to CH3OH [J].

Ashley, Andrew E. ;

Thompson, Amber L. ;

O'Hare, Dermot .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (52) :9839-9843

[5]

Balaraman E, 2011, NAT CHEM, V3, P609, DOI [10.1038/NCHEM.1089, 10.1038/nchem.1089]

[6] Phosphine-boronates: efficient bifunctional organocatalysts for Michael addition [J].

Basle, Olivier ;

Porcel, Susana ;

Ladeira, Sonia ;

Bouhadir, Ghenwa ;

Bourissou, Didier .

CHEMICAL COMMUNICATIONS, 2012, 48 (37) :4495-4497

[7] Decamethylscandocinium-hydrido-(perfluorophenyl)-borate: fixation and tandem tris(perfluorophenyl)-borane catalysed deoxygenative hydrosilation of carbon dioxide [J].

Berkefeld, Andreas ;

Piers, Warren E. ;

Parvez, Masood ;

Castro, Ludovic ;

Maron, Laurent ;

Eisenstein, Odile .

CHEMICAL SCIENCE, 2013, 4 (05) :2152-2162

[8] Tandem Frustrated Lewis Pair/Tris(pentafluorophenyl)borane-Catalyzed Deoxygenative Hydrosilylation of Carbon Dioxide [J].

Berkefeld, Andreas ;

Piers, Warren E. ;

Parvez, Masood .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (31) :10660-10661

[9] On the versatile and unusual coordination behavior of ambiphilic ligands o-R2P(Ph)BR′2 [J].

Bontemps, Sebastien ;

Bouhadir, Ghenwa ;

Miqueu, Karinne ;

Bourissou, Didier .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (37) :12056-12057

[10] Borane-Mediated Carbon Dioxide Reduction at Ruthenium: Formation of C1 and C2 Compounds [J].

Bontemps, Sebastien ;

Vendier, Laure ;

Sabo-Etienne, Sylviane .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (07) :1671-1674

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