N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis

Catalysis by Metal CoMplexes

This book series covers topics of interest to a wide range of academic and industrial chemists, and biochemists. Catalysis by metal complexes plays a prominent role in many processes. Developments in analytical and synthetic techniques and instru-mentation, particularly over the last 30 years, have resulted in an increasingly sophisticated understanding of catalytic processes.

Industrial applications include the production of petrochemicals, fine chemicals and pharmaceuticals (particularly through asymmetric catalysis), hydrometallurgy, and waste-treatment processes. Many life processes are based on metallo-enzyme systems that catalyse redox and acid-base reactions.

Catalysis by metal complexes is an exciting, fast developing and challenging interdisciplinary topic which spans and embraces the three areas of catalysis: heterogeneous, homogeneous, and metallo-enzyme.

Catalysis by Metal Complexes deals with all aspects of catalysis which involve metal complexes and seeks to publish authoritative, state-of-the-art volumes which serve to document the progress being made in this interdisciplinary area of science.

Series Editors

Prof. Claudio Bianchini Institute of Chemistry of Organometallic Compounds,

Polo Scientifico Area Via Madonna del Piano 10 I-50019 Sesto Fiorentino

Italy

Prof D. J. Cole-Hamilton EaStCHEM School of Chemistry

University of St Andrews St Andrews, KY16 9ST

United Kingdom

Prof. Piet W. N. M. van Leeuwen Institute of Chemical Research of Catalonia

Av. Països Catalans 16 Tarragona 43007

Spain

VoluMe 32: N-HeteroCyCliC Carbenes in transition Metal Catalysis

and organoCatalysis

Volume Editor

Catherine S. J. CazinEaStCHEM School of Chemistry

University of St AndrewsSt Andrews, KY16 9ST

United Kingdom

For other titles published in this series, go to www.springer.com/series/5763

Catherine S. J. CazinEditor

N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis

ISBN 978-90-481-2865-5 e-ISBN 978-90-481-2866-2DOI 10.1007/978-90-481-2866-2Springer Dordrecht Heidelberg London New York

Library of Congress Control Number: 2010932004

© Springer Science+Business Media B.V. 2011No part of this work may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission from the Publisher, with the exception of any material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work.

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EditorCatherine S. J. CazinEaStCHEM School of ChemistryUniversity of St AndrewsSt Andrews, KY16 9STUnited Kingdomcc111@st-andrews.ac.uk

v

The origins of amino carbenes as ligands can be traced back almost a century to the complex first synthesised by Tschugajeff (Chugaev). Interestingly, N-heterocyclic carbenes (NHCs) remained a lab curiosity until the mid-1990s. A few years later, this new class of ligands exploded in the literature, so much so that NHCs have become a ubiquitous class of ligands.

During the past decade, NHCs have been coordinated to virtually all transition metals (TM) and studied in numerous catalytic transformations, pushing back the frontiers of catalysis. In this regard, the most salient examples are found in olefin metathesis and cross coupling reactions, and more recently in organocatalysis.

The monograph commences with an introductory overview of NHCs, including a complete description of their steric and electronic properties, that shatters long-standing dogmas such as “phosphine mimicry” and “inexistent pi-acidity”. This sets the stage for catalytic applications that are thoroughly discussed throughout eleven chapters. The penultimate chapter is devoted to decomposition pathways of TM-NHC systems. The closing chapter brings a unique industrial context to this book by describing applications of NHCs in industrial processes, a first of its kind.

In order to provide the reader with a fresh perspective on NHCs, the book has been assembled mainly by young emerging researchers, most of whom studied NHCs in undergraduate classes. This is therefore a perspective from a new genera-tion of researchers that never considered NHCs as laboratory curiosities. A comple-mentary perspective is brought by prominent, well-established academic researchers and an industrialist.

Believe it or not, I have been associated with NHCs in one form or another for the past eleven years. I went through it all, from the frustrations of tar-making to the distress of being scooped past tar-stage. I have even been told to give it all up. For some reason NHCs keep crossing my path, and I find them so intriguing that I keep coming back to them. This book has been an exciting project and I hope it will trigger activity from novices and provide inspiration to researchers already in the field.

St Andrews, UK Catherine S. J. CazinMarch 2010

preface

wwwwwwww

vii

Contents

1 N-Heterocyclic Carbenes: an introductory overview ........................ 1Luigi Cavallo and Catherine S. J. Cazin

2 N-Heterocyclic Carbene Complexes in additions to Multiple bonds .............................................................. 23Andreas A. Danopoulos

3 N-Heterocyclic Carbene Complexes in olefin Metathesis................... 63Xinjun Luan, Reto Dorta, Anita Leitgeb, Christian Slugovc, Sascha Tiede, and Siegfried Blechert

4 N-Heterocyclic Carbene Complexes in polymerisation, oligomerisation and telomerisation reactions ................................... 105David S. McGuinness and Kingsley J. Cavell

5 N-Heterocyclic Carbene Complexes in Cyclisation reactions ............ 131Janis Louie

6 N-Heterocyclic Carbene Complexes in Cross-Coupling reactions .... 157Eloísa Jiménez-Núñez and Manuel Alcarazo

7 N-Heterocyclic Carbene Complexes in arylation reactions other than Cross-couplings ................................................... 191Christophe Berini and Oscar Navarro

8 N-Heterocyclic Carbene Complexes in dehalogenation reactions ....... 207Elena Mas-Marzá, Michael J. Page, and Michael K. Whittlesey

9 N-Heterocyclic Carbene Complexes in reactions involving Carbon Monoxide ................................................. 217Matthew Jeletic and Adam Veige

viii Contents

10 N-Heterocyclic Carbene Complexes in oxidation reactions .............. 237Václav Jurčík and Catherine S. J. Cazin

11 N-Heterocyclic Carbene Complexes in other transition Metal Mediated reactions ................................................... 253Tracy D. Nixon and Jonathan M. J. Williams

12 N-Heterocyclic Carbenes in organocatalysis ....................................... 263Craig D. Campbell, Kenneth B. Ling, and Andrew D. Smith

13 N-Heterocyclic Carbene Complexes: decomposition pathways ......... 299Kingsley J. Cavell and Adrien T. Normand

14 N-Heterocyclic Carbene Complexes in industrial processes .............. 315Oliver Briel and Catherine S. J. Cazin

erratum ...........................................................................................................

index ................................................................................................................. 325

E1

ix

Contributors

Manuel alcarazo Max Planck Institut für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470 Mülheim an der Ruhr, Germany alcarazo@mpi-muelheim.mpg.de

siegfried blechert Technische Universität Berlin, Institut für Chemie, Sekretariat C3, Straße des 17, Juni 135 10623 Berlin, Germany blechert@chem.tu-berlin.de

oliver briel Umicore AG & Co. KG, Rodenbacher Chaussee 4, P.O. Box 1351, 63403 Hanau-Wolfgang, Germany oliver.briel@eu.umicore.com

luigi Cavallo Dipartimento di Chimica, Università di Salerno, Via ponte don Melillo, 84084 Fisciano SA, Italy lcavallo@unisa.it

Kingsley J. Cavell School of Chemistry, Cardiff University, Main Building, Park Place, CF10 3AT Cardiff, UK Cavellkj@cf.ac.uk

Catherine s. J. Cazin EaStCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK cc111@st-andrews.ac.uk

andreas a. danopoulos School of Chemistry, University of Southampton, Highfield SO17 1BJ, UK ad1@soton.ac.uk

x Contributors

reto dorta Organic Chemistry Institute, University of Zurich, Winterthurerstrasse 190, 8057 Zurich, Switzerland dorta@oci.uzh.ch

Janis louie Department of Chemistry, University of Utah, Salt Lake City, Utah 84112-0850, USA louie@chem.utah.edu

david s. Mcguinness School of Chemistry, University of Tasmania, Private Bag 75, Hobart, Tasmania 7000, Australia David.McGuinness@utas.edu.au

oscar navarro Department of Chemistry, University of Hawaii at Manoa, Honolulu, Hawaii 96822, USA oscarnf@hawaii.edu

Christian slugovc Institute for Chemistry and Technology of Materials (ICTM), Graz University of Technology, 8010 Graz, Austria slugovc@tugraz.at

andrew d. smith EaStCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK ads10@st-andrews.ac.uk

adam Veige Department of Chemistry, Center for Catalysis, University of Florida, P.O. Box 117200, Gainesville, FL, USA veige@chem.ufl.edu

Michael K. Whittlesey Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK m.k.whittlesey@bath.ac.uk

Jonathan M. J. Williams Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK j.m.j.williams@bath.ac.uk

xi

abbreviations

Å angstrom(s)AAA Asymmetric Allylic Alkylationacac acetylacetonateACM Asymmetric Cross-MetathesisADMET Acyclic Diene MetathesisAE allyl etheraNHC abnormally bound NHCALTMET Alternating Diene Metathesis PolycondensationAM3 Amphidinol 3Ar arylAROCM Asymmetric Ring Opening Cross MetathesisAT Advanced Technologyatm atmosphere(s)ATRP Atom-Transfer Radical Polymerisationav average

BAr4

F tetrakis[3,5-bis(trifluoromethyl)phenyl]borateBBN borabicyclo[3.3.1]nonyl(Bcat)

2 bis(catecholato)diboron

BDE Bond Dissociation Energyβ-elim. β-eliminationbinap 2,2′-bis(diphenylphosphino)-1,1′-binaphthylbipy 2,2′-bipyridineb:l branched:linear ratiobmim+ 1-n-butyl-3-methylimidazoliumbmiy 1-n-butyl-3-methylimidazolin-2-ylideneBn benzylBoc tert-butoxycarbonyl(Bpin)

2 bis(pinacolato)diborane

Bu butyltBu tert-butylBz benzoyl

xii Abbreviations

ºC degrees Celsiusca. circaCAAC cyclic (alkyl)(amino)carbenescal calorie(s)cat. catalystcf conferCM Cross Metathesiscm-1 wavenumber(s)COD 1,5-cyclooctadieneCOE cycloocteneConv. conversionCp cyclopentadienylCp* 1,2,3,4,5-pentamethylcyclopentadienylCy cyclohexyl

d daysD heatdr diastereomeric ratiodba dibenzylidene acetoneDBM dibenzoylmethaneDBU 1,8-diazabicyclo[5.4.0]undec-7-eneDBP phenyldibenzophospholeDCE 1,2-dichloroethanede diastereomeric excessDec decylDFT Density Functional TheoryDIBAL-H di-iso-butylaluminium hydrideDIPEA diisopropylethylamine (Hunig’s base)DMA dimethylacetamideDME dimethoxyethaneDMF dimethylformamideDMI 1,3-dimethyl-2-imidazolidinonedmpe dimethylphosphinoethaneDMSO dimethylsulphoxideDPC diphenyl carbonatedppe (diphenylphosphino)ethanedppf (diphenylphosphino)ferrocenedppp 1,3-bis(diphenylphosphino)propanedr diastereomeric ratiodvds 1,3-divinyltetramethyldisiloxanedvtms divinyltetramethylsiloxane

E1/2

half-wave potentialE

act activation energy

ECM Enyne Cross MetathesisEDA ethyldiazoacetate

xiiiAbbreviations

ee enantiomeric excesse.g. for exampleemim+ 1-ethyl-3-methylimidazoliumemiy 1- ethyl-3-methylimidazolin-2-ylideneEnt enantiomericequiv equivalentEt ethylet al. et aliiEWG Electron Withdrawing Group

Fc ferrocenylFDA US Food and Drug Administration

g gram(s)GC Gas Chromatographygem geminalGSK Glaxo Smith Kline

h hour(s)Hbbtm bis-{benzothiazol-2-yl}methaneHBpin pinacolboraneHCV Hepatitis C VirusHex hexylHMDS hexamethyldisilazaneHNBR Hydrogenated Nitrile Butadiene RubbersHOAt 1-hydroxy-7-azabenzotriazoleHOBt hydroxybenzotriazoleHz Hertz

IAd 1,3-diadamantylimidazoliumICy N,N’-(dicyclohexyl)imidazol-2-ylideneIDTB N,N’-bis-[2,5-(di-tert-butyl)phenyl]imidazol-2-ylidenei.e. id estIiPr N,N’-(di-iso-propyl)imidazol-2-ylideneIL Ionic LiquidIm ImidazoliumIMe N,N’-(dimethyl)imidazol-2-ylideneIMes N,N’-bis-[2,4,6-(trimethyl)phenyl]imidazol-2-ylideneInc. IncorporatedIND Investigational New DrugIP Intellectual PropertyIPr N,N’-bis-[2,6-(di-iso-propyl)phenyl]imidazol-2-ylideneIR InfraredItBu N,N’-(di-tert-butyl)imidazol-2-ylideneITM 1,3,4,5-tetramethylimidazol-2-ylideneITmt N,N’-bis(2,2”,6,6”-tetramethyl-m-terphenyl-5’-yl)imidazole-

2-ylidene

xiv Abbreviations

ITol N,N’-bis-(4-methylphenyl)imidazol-2-ylideneJ coupling constantJ joule(s)

k kilo

L litre(s)Load. loading

μ microM molarM metalm millim metaMAH maleic anhydrideMALDI-TOF MS Matrix-Assisted Laser Desorption Ionisation Time-Of-Flight

Mass SpectrometryMAO methylaluminoxaneMe methylMes mesityl (2,4,6-trimethylphenyl)min. minutesMMA methyl methacrylateMMAO modified methylaluminoxaneMOM methoxymethyletherMS Molecular SievesmV millivolt

n normalnbd norbornadieneNHC N-Heterocyclic CarbeneNMO N-methylmorpholine-N-oxideNMP N-methyl-2-pyrrolidoneNMR Nuclear Magnetic Resonnance

o orthoOAc acetateOTf trifluoromethanesulfonate

p paraPCBs polychlorinated biphenylsPCs polycarbonatesPG Protecting GroupPh phenylPiv pivaloylPOPs Persistent Organic PollutantsPr propyliPr iso-propylPh phenyl

xvAbbreviations

pin pinacolPiv pivaloylPMP para-methoxyphenylppm parts per millionpsi pound per square inch

quant. quantitative

rac racemicRCM Ring Closing MetathesisR. E. Reductive Elimination (Red. Elim.)Ref referenceREMP Ring Expansion Metathesis PolymerisationROCM Ring Opening Cross MetathesisROIMP Ring Opening Insertion Metathesis PolymerisationROMP Ring Opening Metathesis PolymerisationRRM Ring Rearrangement Metathesisrt room temperature

SEM 2-(trimethylsilyl)ethoxy-methylSICy N,N’-(dicyclohexyl)imidazolidin-2-ylideneSIEt N,N’-(diethyl)imidazolidin-2-ylideneSIMes N,N’-bis[2,4,6-(trimethyl)phenyl]imidazolidin-2-ylideneSIPr N,N’-bis[2,6-(diisopropyl)phenyl]imidazolidin-2-ylideneSubstr. substratesyngas synthesis gas CO:H

2 mixture

T temperatureTASF tris(dimethylamino)sulfonium difluorotrimethylsilicateTBAF tetra-n-butylammonium fluorideTBDPS tert-butyldiphenylsilylTBHP tert-butyl hydroperoxideTBS tert-butylsilylTEP Tolman Electronic ParameterTES triethylsilylTf trifluoromethanesulfonyl (triflyl)TFA trifluoroacetic acidTFAA trifluoroacetic anhydridethf tetrahydrofuranTIMEN tris[2-(3-alkylimidazol-2-ylidene)ethyl]amineTM Transition MetalTMHD 2,2,6,6-tetramethyl-3,5-heptanedionatetmiy 1,3,4,5-tetramethylimidazol-2-ylideneTMPDA tetramethylpropylenediamineTMS trimethylsilylTOF Turnover FrequencyTol tolyl

xvi Abbreviations

TON Turnover NumberTS Transition StateTs para-toluenesulfonyl (tosyl)

νav

average value of stretching frequencies in IR%V

Bur Percent Volume Buried