Table Of ContentTopics in Current Chemistry 372
Takeo Kawabata Editor
Site-Selective
Catalysis
372
Topics in Current Chemistry
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Takeo Kawabata
Editor
Site-Selective Catalysis
With contributions by
(cid:1) (cid:1) (cid:1) (cid:1)
M. Canta M. Costas M.W. Giuliano M. Kanai
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
T. Kawabata M.J. Krische K. Manabe S.J. Miller J. Ni
T. Ooi (cid:1) M. Rodr´ıguez (cid:1) I. Shin (cid:1) M.S. Taylor (cid:1) Y. Ueda (cid:1)
(cid:1)
D. Uraguchi M. Yamaguchi
Editor
TakeoKawabata
InstituteforChemicalResearch
KyotoUniversity
Kyoto
Japan
ISSN0340-1022 ISSN1436-5049 (electronic)
TopicsinCurrentChemistry
ISBN978-3-319-26331-1 ISBN978-3-319-26333-5 (eBook)
DOI10.1007/978-3-319-26333-5
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Preface
Chemoselectivityandstereoselectivityhavebeenkeyfactorsinthedevelopmentof
fineorganicsynthesis.Inadditiontotheseselectivities,site-selectivityhasrecently
beenreceivingmuchattention,becausesite-selectivecatalysisenablesconvention-
ally difficult molecular transformations such as late-stage functionalization of
biologically active complex molecules, which provides straightforward access to
structurallydiversecompoundswithrelatedbiologicalactivity.However,methods
for site-selective molecular transformation of complex molecules have not been
wellexplored.Thismaybebecauseofthelackofreliablestrategyforsite-selective
catalysis. Recently, site-selective catalysis has been expanding its scope and sig-
nificanceasanewchallengeinorganicsynthesistorealizeconventionallydifficult,
yetvaluablemoleculartransformations.
During the last few decades, asymmetric synthesishas been extensively devel-
oped.“Stericapproachcontrol”isthekeyprinciplefortheextensivedevelopment
of asymmetric synthesis. For example, if one of the two potentially reactive
enantiofaces is effectivelyshielded bystericinteraction, ahighlyenantioselective
reaction would be expected. On the other hand, this principle seems not to be
effective for achieving site-selective molecular transformation of complex mole-
cules because, to functionalize a desirable reactive site, the remaining many
undesirable potentially reactive sites have to be sterically shielded by the catalyst
orthereagent.Oneofthepromisingapproachestoachievesite-selectivefunctiona-
lizationmaybetakingadvantageoftheaccelerationofthereactionatthedesirable
site based on precise molecular recognition with the properly designed catalyst,
rather than the deceleration of the reactions at many undesirable sites by steric
shielding. Undersuch catalyst-controlledconditions,selective moleculartransfor-
mation is expected to take place at the desirable site independently from the
intrinsicreactivityofthesubstrate.
From these scientific backgrounds, this book focuses on (1) ligand-controlled
site-selectivecross-coupling,(2)iron-catalyzedsite-selectiveoxidationofalkylC–
Hbonds,(3)catalyticsite-selectiveconjugateadditionofconjugateddienonesand
trienones,(4)site-selectiveredox-triggeredC–Ccouplingofdiols,(5)site-selective
v
vi Preface
cleavage of peptides and proteins, (6) catalyst-controlled site-selective molecular
transformations of carbohydrates, (7) site-selective functionalization of complex
natural products by peptide-based catalysts, and (8) site-selective acylation of
carbohydrates and its application to unconventional retrosynthesis of natural
glycosides.
Site-selectivemoleculartransformationscanbeperformedineitherasubstrate-
controlledoracatalyst-controlledmanner,atleastinprinciple.Morearbitraryand
diverse molecular transformation is expected, especially by such catalyst-con-
trolledtransformations.Themolecularrecognitionprocesswithitsdynamicnature
seems to be responsible for the performance of catalyst-controlled site-selective
molecular transformation. Various examples of catalyst-controlled site-selective
functionalization and its application to biological active natural products with
complex structures are described. We know, however, that we are still at the
preliminary stage in this emerging scientific field of site-selective catalysis. I
believe that publication of this book can stimulate extensive development of
methodsforthesefuture-orientedmoleculartransformations.
Uji,Kyoto,Japan TakeoKawabata
2015
Contents
Ligand-ControlledSite-SelectiveCross-Coupling. . . . . . . . . . . . . . . . . . 1
MiyukiYamaguchiandKeiManabe
RecentAdvancesintheSelectiveOxidationofAlkylC–HBonds
CatalyzedbyIronCoordinationComplexes. . . . . . . . . . . . . . . . . . . . . . 27
Merce` Canta,Mo`nicaRodr´ıguez,andMiquelCostas
Site-SelectiveConjugateAdditionThroughCatalyticGeneration
ofIon-PairingIntermediates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
DaisukeUraguchiandTakashiOoi
AsymmetricIridium-CatalyzedC–CCouplingofChiralDiols
viaSite-SelectiveRedox-TriggeredCarbonylAddition. . . . . . . . . . . . . 85
InjiShinandMichaelJ.Krische
Site-SelectivePeptide/ProteinCleavage. . . . . . . . . . . . . . . . . . . . . . . . . 103
JizhiNiandMotomuKanai
Catalyst-Controlled,RegioselectiveReactionsofCarbohydrate
Derivatives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
MarkS.Taylor
Site-SelectiveReactionswithPeptide-BasedCatalysts. . . . . . . . . . . . . . 157
MichaelW.GiulianoandScottJ.Miller
OrganocatalyticSite-SelectiveAcylationofCarbohydrates
andPolyolCompounds. . . . .. . . . .. . . . . .. . . . .. . . . .. . . . .. . . . . .. 203
YoshihiroUedaandTakeoKawabata
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
vii
TopCurrChem(2016)372:1–26
DOI:10.1007/128_2015_654
#SpringerInternationalPublishingSwitzerland2015
Publishedonline:2August2015
Ligand-Controlled Site-Selective
Cross-Coupling
MiyukiYamaguchiandKeiManabe
Abstract Site-selective mono-cross-coupling reactions involving dichloro- or
dibromo(hetero)aryl substrates are utilized to prepare substituted monochloro- or
monobromo(hetero)arenes,which areusedasdrugcomponents andsyntheticpre-
cursors.Inthesereactions,selectivitytowardthepreferredreactionsiteofadihalo
(hetero)arene can vary depending on the ancillary ligand of the transition metal
catalyst. This review summarizes the examples of ligand-controlled site-selective
cross-couplingreactions,specificallythosemediatedbyPdcomplexes.
Keywords Kumada–Tamao–Corriu coupling (cid:129) Palladium (cid:129) Sonogashira
coupling(cid:129)Suzuki–Miyauracoupling(cid:129)Transitionmetalcatalyst
Contents
1 Introduction................................................................................... 2
2 Suzuki–MiyauraCoupling................................................................... 4
3 Kumada–Tamao–CorriuCoupling........................................................... 12
4 SonogashiraCoupling........................................................................ 17
5 Conclusion.................................................................................... 23
References........................................................................................ 23
Abbreviations
Ar Aryl
Cy Cyclohexyl
M.YamaguchiandK.Manabe(*)
SchoolofPharmaceuticalSciences,UniversityofShizuoka,52-1Yada,Suruga-ku,
Shizuoka422-8526,Japan
e-mail:[email protected]
2 M.YamaguchiandK.Manabe
dba Dibenzylideneacetone
DHTP Dihydroxyterphenylphosphine
DPEPhos Bis[2-(diphenylphosphino)phenyl]ether
DPPF 1,10-Bis(diphenylphosphino)ferrocene
HTP Hydroxyterphenylphosphine
LUMO Lowestunoccupiedmolecularorbital
NMP N-Methylpyrrolidone
PMP 4-Methoxyphenyl
PXPd2 Dichloro(chlorodi-tert-butylphosphine)palladium(II)dimer
Q-Phos 1,2,3,4,5-Pentaphenyl-10-(di-tert-butylphosphino)ferrocene
TBAC Tetrabutylammoniumchloride
Th Thienyl
Tol 4-Methylphenyl
Ts Tosyl,p-toluenesulfonyl
Xantphos 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene
XPhos 2-Dicyclohexylphosphino-20,40,60-triisopropylbiphenyl
1 Introduction
Cross-coupling reactions between organic halides (or pseudohalides such as
triflates) with organometallic reagents are among the most important transition
metal-catalyzedtransformations andhave various synthetic applicationsinacade-
mia and industry [1–3]. Recently, organic dihalides, which are molecules
containing two halo substituents, have attracted considerable interest as cross-
coupling substrates. For example, double-cross-coupling of organic dihalides
affords disubstituted compounds, whereas mono-cross-coupling of dihalides
affordsmonohalogenatedcompounds.Thelatterareversatilesyntheticintermedi-
ates exhibiting interesting structural motifs and have therefore inspired efforts to
developefficientmethodsformono-cross-couplingreactions.
Selectivity between the two halo groups in organic dihalide substrates is an
important topic which needs to be considered in the chemistry of mono-cross-
coupling reactions. For instance, chemoselective cross-coupling between two dif-
ferent halo groups is easily achieved through the intrinsic reactivity order of halo
groups (i.e., I>Br>Cl>F) [4–7], but site-selective cross-coupling between two
identical halo groups is more challenging (Scheme 1, X¼X0). The latter
Scheme1 Chemoselective R R R
catalyst
andsite-selectivecross- R' M
couplingoforganic X R' or X
dihalides
X' X' R'
X, X' = halogen
X = X' : chemoselective cross-coupling
X = X' : site-selective cross-coupling
