Rhodium Catalysis

291 Pages·2018·18.16 MB·English

by  Carmen Claver (eds.)

Topics in Organometallic Chemistry 61
Carmen Claver Editor
Rhodium
Catalysis
61
Topics in Organometallic Chemistry
Editorial Board
M. Beller, Rostock, Germany
P.H. Dixneuf, Rennes CX, France
J. Dupont, Porto Alegre, Brazil
A. Fu¨rstner, Mu¨lheim, Germany
F. Glorius, Mu¨nster, Germany
L.J. Gooßen, Kaiserslautern, Germany
T. Ikariya, Tokyo, Japan
S.P. Nolan, Ghent, Belgium
J. Okuda, Aachen, Germany
L.A. Oro, Zaragoza, Spain
M. Willis, Oxford, United Kingdom
Q.-L. Zhou, Tianjin, China
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Carmen Claver
Editor
Rhodium Catalysis
With contributions by
(cid:1) (cid:1) (cid:1) (cid:1)
D. Bonincontro A.J. Burnie R. Castarlenas M. Cettolin
(cid:1) (cid:1) (cid:1) (cid:1)
A.B. Cuenca A. Cunillera J.G. de Vries P.A. Evans
E. Ferna´ndez (cid:1) E.J. Garc´ıa-Sua´rez (cid:1) A.D. Giuseppe (cid:1)
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
C. Godard K. Kahr P. Kalck L.A. Oro P. Puylaert
E.A. Quadrelli (cid:1) A. Riisager (cid:1) A. Ruiz (cid:1) M. Urrutigo¨ıty
Editor
CarmenClaver
FacultatdeQu´ımica
UniversitatRoviraiVirgili
Tarragona,Spain
ISSN1436-6002 ISSN1616-8534 (electronic)
TopicsinOrganometallicChemistry
ISBN978-3-319-66663-1 ISBN978-3-319-66665-5 (eBook)
DOI10.1007/978-3-319-66665-5
LibraryofCongressControlNumber:2017953213
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Preface
Rhodiumcoordinationcomplexesorsystemsformedwithrhodiuminthepresence
of ligands, in particular phosphorus derivatives, have been extensively and suc-
cessfullyusedascatalyticprecursorsinhomogeneouscatalysisformanyyears.The
particular properties of both oxidation states of Rh(I) and Rh(III) allow for the
successive oxidative addition, insertion, reductive elimination steps,and facilitate
the activity and efficiency of the rhodium catalysts. The selectivity can be con-
trolled and modified due to the versatility and modification possibilities of the
ligandscoordinatedtotherhodiumcenter.Afterthebreakthroughoftheapplication
of RhCl(PPh ) as a hydrogenation catalyst, rhodium catalysis blossomed enor-
3 3
mouslyandcationicrhodium(I)phosphorussystemswerealsoappliedinhydroge-
nation reactions, being particularly attractive due to the use of chiral ligands
allowing for the enantioselective hydrogenation reaction of prochiral substrates.
The main characteristic of catalytic rhodium systems is the high selectivity and
enantioselectivity achieved in most of the homogeneous catalytic processes. A
relevant example is the hydroformylation reaction which involves a one-carbon
chain elongation by the addition of carbon monoxide and hydrogen across a C=C
double bond. It is well known that this is one of the main industrial processes
carriedoutbyhomogeneouscatalysisconcerningtheformationofaldehydesfrom
alkenes.Theuseoftheappropriateligandsallowsthecontroloftheregioselectivity
andmorerecentlythecontroloftheenantioselectivity.
Manyrelevantbooksandreviewshavebeenpublishedaboutrhodium-catalyzed
processes. This new volume “Rhodium catalysis” in the series “Topics in Organ-
ometallicChemistry”intendstobeanupdateofrelevant,well-knownreactions,as
wellasasummaryofthelesserknownapplicationsofrhodiumcatalysisinorganic
transformations,togetherwithtopicsrelatedwithsustainability.Allthechaptersare
authoredbyresearchexpertsineachoneofthetopicspresented.
It is shown in this volume how for hydrogenation reactions the monodentate
ligandsprovideopportunitiesthatwouldhavebeenimpossibletoimaginewiththe
bidentate ligands, owing to the possibility of producing complexes based on two
different ligands. Rhodium-catalyzed C–H and C–X borylation is extensively
reviewed in this volume. This area has received growing interest based on the
v
vi Preface
strong influence of rhodium to activate H–B and B–B bonds, the power of the
ligandsthatmodifytherhodiumcentertoinducehighlevelsofchemo-,regio-,and
enantioselectivity, and the unrestricted mechanisms that can be deduced with the
aidofdensityfunctionaltheory(DFT)calculations.
The impressive advances observed in recent years in the field of asymmetric
hydroformylation are examined in this volume and conclude that the key to
achievinghighenantioselectivitiesisnotthetypeofphosphorusfunctioninvolved
inthecoordinationtothemetal,butrathertheparticularspatialarrangementofthe
coordinated ligand. Supramolecular strategies which have been very successfulin
asymmetrichydroformylationarealsoconsidered,indicatingthatthecontrolofthe
second coordination sphere could be the key to achieving selectivity for the more
challengingsubstrates.
Tandem reactions demonstrate how the efficiency of the reaction is improved
whenoperatingintheabsenceofisolatingtheintermediates,leadingtotheforma-
tion ofmorecomplex moleculesinan economicmanner. Itis showninthis work
how the rhodium-catalyzed tandem carbonylation reactions, involving the
hydroformylation of an alkene followed by the transformation of the aldehyde
productwithasecondreagent,canyieldimportantchemicalsfororganicsynthesis.
Otherreactionsareincludedinthisvolume,forexampletherhodium-catalyzed
decarbonylationdevelopedoverthelast50yearswhichhasresultedinawiderange
of reported catalyst systems and reaction protocols. The applications of these
rhodium-catalyzeddecarbonylationreactionsaresurveyedanddiscussed,including
cross-couplingreactions,tandemreactions,andalternativemethodologiesforpro-
cess intensification. The advances in rhodium-catalyzed cyclocarbonylation reac-
tionsarealsodiscussed,includingavarietyofmethodsforthesynthesisofcarbo-
and heterocyclic rings of different sizes, diastereoselective and asymmetric
approaches, and the application of these reactions in the total synthesis of the
important natural products (+)-asteriscanolide and (–)-ingenol. Rhodium catalysis
for C–S bond formation is also considered. The recent developments in the reac-
tionsofcross-coupling,C–Hactivation,metathesis,thiolation,carbothiolation,and
hydrothiolation for the C–S bond formation catalyzed by rhodium complexes,
particularlyhighlightingthesyntheticandmechanisticaspects,aresummarized.
This volume also includes a chapter discussing the role of rhodium-based
catalysts in homogenous and heterogeneous catalyzed CO reductions, with well-
2
describedmechanisms.
Thisworkpresentstheadvances,newperspectives,andapplicationsinavariety
of representative rhodium-catalyzed reactions and will therefore be useful for
researchers, graduate students, and synthetic chemists at all levels in academia
andindustry.
Tarragona,Spain CarmenClaver
Contents
Rhodium-CatalyzedC–BBondFormation. . . . . . . . . . . . . . . . . . . . . . . 1
AnaB.CuencaandElenaFerna´ndez
RhodiumCatalystsforC–SBondFormation. . . . . . . . . . . . . . . . . . . . . 31
AndreaDiGiuseppe,RicardoCastarlenas,andLuisA.Oro
TandemRhodiumCarbonylationReactions. . . . . . . . . . . . . . . . . . . .. . 69
PhilippeKalckandMartineUrrutigo¨ıty
AsymmetricHydroformylationUsingRhodium. . . . . . . . . . . . . . . . . . . 99
AntonCunillera,CyrilGodard,andAuroraRuiz
RhodiumCatalyzedDecarbonylation. . . . . . . . . . . . . . . . . . . . . . . . . . . 145
EduardoJ.Garc´ıa-Sua´rez,KlaraKahr,andAndersRiisager
RecentDevelopmentsinRhodium-CatalyzedCyclocarbonylation
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
AndrewJ.BurnieandP.AndrewEvans
Rhodium-CatalysedHydrogenationsUsingMonodentateLigands. . . . . 231
MattiaCettolin,PimPuylaert,andJohannesG.deVries
CO ReductionReactionsbyRhodium-BasedCatalysts. . . . . . . . . . . . . 263
2
DaniloBonincontroandElsjeAlessandraQuadrelli
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
vii
TopOrganometChem(2018)61:1–30
DOI:10.1007/3418_2016_168
#SpringerInternationalPublishingSwitzerland2016
Publishedonline:29May2016
Rhodium-Catalyzed C–B Bond Formation
AnaB.CuencaandElenaFerna´ndez
Abstract This chapter focuses on Rh-activation of boron-based reagents and its
assistance in efficient catalytic borylation reactions. The introduction is a critical
reflectionoftheimportancethathydroboranereagentshavehadinreactionssuchas
Rh-catalyzed hydroboration for the last 30 years. The next section shows a brief
history of the Rh–B bond formation from Rh complexes and diboron reagents.
The most relevant advances in Rh-catalyzed diboration are summarized in the
following section. In the fourth section, examples of Rh-catalyzed β-boration of
α,β-unsaturatedsubstratesarecollected,completingthefifthsectionwithadescrip-
tionandcommentsaboutthenewtrendsonRh-catalyzedC–HandC–Xborylation.
Attheendofthischapter,theauthorscompileasummaryandtheirperspectivefor
therelatedfieldfromamechanisticpointofview.
Keywords Borylation(cid:129)Catalysis(cid:129)C–Bbond(cid:129)Rhodium(cid:129)Stereoselectivity
Contents
1 Introduction:30YearsonRh-CatalyzedHydroboration................................... 2
2 ActivationofDiboronReagentsbyRhodiumComplexes.................................. 5
2.1 Rh-ActivationofDiboronReagentsbyOxidativeAddition......................... 5
2.2 Rh-ActivationofDiboronReagentsbyσ-BondMetathesis.......................... 10
3 Rh-CatalyzedDiborationReaction.......................................................... 11
3.1 Rh-CatalyzedDiborationReactionofC–CMultipleBonds......................... 11
3.2 Rh-CatalyzedDiborationReactionofC–XMultipleBonds......................... 18
4 Rh-Catalyzedβ-Borationofα,β-UnsaturatedCarbonylCompounds....................... 18
A.B.CuencaandE.Ferna´ndez(*)
FacultyofChemistry,UniversityRoviraiVirgili,C/Marcell´ıDomingos/n,43007Tarragona,
Spain
e-mail:[email protected];[email protected]
2 A.B.CuencaandE.Ferna´ndez
5 Rh-CatalyzedC–HandC–X(X¼F,CN,OMe)BorylationwithDiboronReagents..... 20
6 SummaryandOutlook....................................................................... 26
References........................................................................................ 26
1 Introduction: 30 Years on Rh-Catalyzed Hydroboration
The first isolation of a σ-rhodium–boron complex was carried by Kono et al. [1]
(Scheme1)despitethefactthatseveralpreviousattemptswereconductedtoreact
rhodium complexes with series of carboranes and polyboranes [2–6]. The
hydroboranereagentsselectedbyH.Konoandco-workerswerethecyclicsecond-
ary boronate esters catecholborane (HBcat) and neopentylborane (HBneop). The
complex [RhX(PPh ) ] (X¼Cl, Br) was able to activate the B–H bond of HBcat
3 3
andHBneopviaoxidativeaddition.Thatearlykeyexperimentledtotheeventual
development of rhodium-complex-catalyzed hydroboration of alkenes. The first
examplesofthis type ofcatalysis(Scheme 2)corroborated the potential power of
the original experiment [7, 8]. In particular the use of catecholborane, by Mannig
andNoth[7],wasthemodelonwhichmostfurtherexperimentationhasbeenbased
(Scheme 2b). Burgess and Ohlmeyer were the first to demonstrate catalytic
H H B O H B O H
PPhh33PP RChl B OO O Ph3PX Rh PPPPhh33 O PPhh33PP RChl B OO
1b 1(X=Cl,Br) 1a
Scheme1 Firstisolatedσ-rhodium–boroncomplex
a
b
Scheme2 FirstRh-catalyzedhydroboration