Mechanistic Insights into a Supramolecular Self-Assembling Catalyst System: Evidence for Hydrogen Bonding during Rhodium-Catalyzed Hydroformylation

被引：70

作者：

Gellrich, Urs ^{[1
]}

Seiche, Wolfgang ^{[1
]}

Keller, Manfred ^{[1
]}

Breit, Bernhard ^{[1
]}

机构：

[1] Univ Freiburg, Freiburg Inst Adv Studies FRIAS, Inst Organ Chem & Biochem, D-79104 Freiburg, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2012年 / 51卷 / 44期

关键词：

DFT calculations; hydroformylation; hydrogen bonds; IR spectroscopy; self-assembly; TRANSITION-METAL CATALYSTS; REGIOSELECTIVE HYDROFORMYLATION; BIDENTATE LIGANDS; SELECTIVITY; REACTIVITY; ALKENES;

D O I：

10.1002/anie.201203768

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The structural integrity and flexibility provided by intermolecular hydrogen bonds leads to the outstanding properties of the 6- diphenylphosphinopyridin-(2H)-1-one ligand (see scheme) in the rhodium-catalyzed hydroformylation of terminal alkenes, as demonstrated by the combination of spectroscopic methods and DFT computations. Hydrogen bonds were also detected in a competent intermediate of the catalytic cycle. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：11033 / 11038

页数：6

共 45 条

[1] Domino hydroformylation/enantioselective cross-aldol addition [J].

Abillard, Olivier ;

Breit, Bernhard .

ADVANCED SYNTHESIS & CATALYSIS, 2007, 349 (11-12) :1891-1895

[2]

[Anonymous], 2007, ANGEW CHEM

[3] Online Monitoring of Hydroformylation Intermediates by ESI-MS [J].

Beierlein, Christian H. ;

Breit, Bernhard ;

Schmidt, Roberto A. Paz ;

Plattner, Dietmar A. .

ORGANOMETALLICS, 2010, 29 (11) :2521-2532

[4]

Billig E., 1988, US Patent, Patent No. [4,769,498, 4769498]

[5] Hydrogen bonding as a construction element for bidentate donor ligands in homogeneous catalysis: Regioselective hydroformylation of terminal alkenes [J].

Breit, B ;

Seiche, W .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (22) :6608-6609

[6]

Breit B, 2001, SYNTHESIS-STUTTGART, P1

[7] Recent advances in alkene hydroformylation [J].

Breit, Bernhard .

METAL CATALYZED REDUCTIVE C-C BOND FORMATION: A DEPARTURE FROM PREFORMED ORGANOMETALLIC REAGENTS, 2007, 279 :139-172

[8] OBSERVATION OF DICARBONYLDIPHOSPHINERHODIUM HYDRIDES AND THEIR OLEFIN-TRAPPING ABILITY [J].

BROWN, JM ;

CANNING, LR ;

KENT, AG ;

SIDEBOTTOM, PJ .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1982, (13) :721-723

[9] Unraveling the origin of regioselectivity in rhodium diphosphine catalyzed hydroformylation.: A DFT QM/MM study [J].

Carbó, JJ ;

Maseras, F ;

Bo, C ;

van Leeuwen, PWNM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (31) :7630-7637

[10] (CHELATING DIPHOSPHINE)RHODIUM-CATALYZED DEUTERIOFORMYLATION OF 1-HEXENE - CONTROL OF REGIOCHEMISTRY BY THE KINETIC RATIO OF ALKYLRHODIUM SPECIES FORMED BY HYDRIDE ADDITION TO COMPLEXED ALKENE [J].

CASEY, CP ;

PETROVICH, LM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (22) :6007-6014

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