Organic reaction mechanisms 2013: an annual survey covering the literature dated January to December 2013

713 Pages·2016·19.2 MB·English

by  Knipe, A. C

⋅
ORGANIC REACTION MECHANISMS 2013
ORGANIC REACTION
⋅
MECHANISMS 2013
An annual survey covering the literature
dated January to December 2013
Editedby
A.C.Knipe
University ofUlster
Northern Ireland
Thiseditionfirstpublished2017
©2017JohnWiley&Sons,Ltd
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Contributors
C.T.BEDFORD DepartmentofChemistry,UniversityCollegeLondon,
20GordonStreet,London,WC1H0AJ,UK
M.L.BIRSA FacultyofChemistry,“Al.I.Cuza”UniversityofIasi,
Bd.CarolI,11,Iasi700506,Romania
S.CHASSAING CentreNationaldelaRechercheScientifique,Université
deToulouse,Toulouse,France
CentrePierrePotier,ITAV,UniversitédeToulouse,
F-31106Toulouse,France
INSA,F-31400Toulouse,France
J.M.COXON DepartmentofChemistry,UniversityofCanterbury,
Christchurch,NewZealand
M.R.CRAMPTON DepartmentofChemistry,UniversityofDurham,South
Road,Durham,DH13LE,UK
N.DENNIS 3CamphorlaurelCourt,Stretton,Brisbane,Queensland
4116,Australia
E.GRAS LaboratoiredeChimiedeCoordination,CentreNational
delaRechercheScientifique,205RoutedeNarbonne
31077,ToulouseCedex4,France
D.A.KLUMPP DepartmentofChemistry,NorthernIllinoisUniversity,
DeKalb,IL60115,USA
A.C.KNIPE FacultyofLifeandHealthSciences,UniversityofUlster,
Coleraine,NorthernIreland
P.KOCˇOVSKY´ DepartmentofOrganicChemistry,ArrheniusLaboratory,
StockholmUniversity,StockholmSE10691,Sweden
DepartmentofOrganicChemistry,CharlesUniversity,
12843Prague2,CzechRepublic
R.N.MEHROTRA DepartmentofChemistry,JaiNarainVyasUniversity,
A-85SaraswatiNagar,Jodhpur342005,India
B.A.MURRAY DepartmentofScience,InstituteofTechnology,Tallaght
(ITTDublin),DublinD24FKT9,Ireland
K.C.WESTAWAY DepartmentofChemistryandBiochemistry,Laurentian
University,Sudbury,OntarioP3E2C6,Canada
v
Preface
Thepresentvolume,theforty-ninthintheseries,surveysresearchonorganicreaction
mechanismsdescribedintheavailableliteraturedated2013.Inordertolimitthesizeof
thevolume,itisnecessarytoexcludeorrestrictoverlapwithotherpublicationswhich
reviewspecialistareas(e.g.photochemicalreactions,biosynthesis,enzymology,electro-
chemistry,organometallicchemistry,surfacechemistryandheterogeneouscatalysis).In
ordertominimizeduplication,whileensuringacomprehensivecoverage,theeditorcon-
ductsasurveyofallrelevantliteratureandallocatespublicationstoappropriatechapters.
Whileaparticularreferencemaybeallocatedtomorethanonechapter,itisassumedthat
readerswillbeawareofthealternativechapterstowhichaborderlinetopicofinterest
mayhavebeenpreferentiallyassigned.
In view of the considerable interest in application of stereoselective reactions to
organicsynthesis,wenowprovideindication,inthemargin,ofreactionswhichoccur
withsignificantdiastereomericorenantiomericexcess(deoree).
WewelcomeProfDougKlumppasauthorofthecarbocationchapter.HereplacesProf
BobMcClellandwhohasprovidedexpertreviewsofthisareasinceORM2000andnow
deservessomewell-earnedrespite.Wearenaturallypleasedtohaveretainedmembers
ofourcurrentteamofexperiencedauthorsforallotherchaptersofORM2013.
Although every effort has again been made to reduce the delay between title year
and publication date, circumstances beyond the editor’s control resulted in late arrival
of a substantial chapter which made it impossible to regain our optimum production
schedule.
I wish to thank the staff of John Wiley & Sons and our expert contributors for their
effortstoensurethatthereviewstandardsofthisseriesaresustained.Weareawareof
demands of informatic evolution which require periodic adjustment of our procedures
andarenotalwayshelpful!
A.C.K.
vii
Contents
1. ReactionsofAldehydesandKetonesandTheirDerivatives
byB.A.Murray....................................................... 1
2. Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and Their
DerivativesbyC.T.Bedford........................................... 67
3. OxidationandReductionbyR.N.Mehrotra............................ 91
4. CarbenesandNitrenesbyE.GrasandS.Chassaing..................... 177
5. AromaticSubstitutionbyM.R.Crampton.............................. 217
6. CarbocationsbyD.A.Klumpp........................................ 273
7. NucleophilicAliphaticSubstitutionbyK.C.Westaway.................. 321
8. CarbanionsandElectrophilicAliphaticSubstitutionbyM.L.Birsa..... 361
9. EliminationReactionsbyM.L.Birsa.................................. 383
10. AdditionReactions:PolarAdditionbyP.Kocˇovsky´..................... 393
11. AdditionReactions:CycloadditionbyN.Dennis ....................... 483
12. MolecularRearrangementsbyJ.M.Coxon............................ 519
AuthorIndex......................................................... 609
SubjectIndex........................................................ 651
ix
CHAPTER1
Reactions of Aldehydes and Ketones
and Their Derivatives
B.A.Murray
DepartmentofScience,InstituteofTechnology,Tallaght(ITTDublin),
Dublin,Ireland
FormationandReactionsofAcetalsandRelatedSpecies . . . . . . . . . . . . . . 2
ReactionsofGlucosides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
ReactionsofKetenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
FormationandReactionsofNitrogenDerivatives. . . . . . . . . . . . . . . . . . . 7
Imines:Synthesis,andGeneralandIminiumChemistry . . . . . . . . . . . . . 7
Mannich,Mannich-typeandNitro-MannichReactions. . . . . . . . . . . . . . 8
Other‘Name’ReactionsofImines . . . . . . . . . . . . . . . . . . . . . . . . 11
SynthesisofAzacyclopropanesfromImines . . . . . . . . . . . . . . . . . . . 13
AlkylationsandAdditionsofOtherC-NucleophilestoImines . . . . . . . . . . 13
Arylations,AlkenylationsandAllylationsofImines . . . . . . . . . . . . . . . 14
MiscellaneousAdditionstoImines . . . . . . . . . . . . . . . . . . . . . . . . 15
ReductionofImines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
OtherReactionsofImines. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Oximes,HydrazonesandRelatedSpecies . . . . . . . . . . . . . . . . . . . . 19
C–CBondFormationandFission:AldolandRelatedReactions . . . . . . . . . . 23
ReviewsofAldolsandGeneralReviewsofAsymmetricCatalysis . . . . . . . 23
AsymmetricAldolsCatalysedbyProlineandItsDerivatives . . . . . . . . . . 24
AsymmetricAldolsCatalysedbyOtherOrganocatalysts . . . . . . . . . . . . . 24
TheMukaiyamaAldol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
OtherAsymmetricAldols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
TheHenry(Nitroaldol)Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 28
TheBaylis–HillmanReactionandItsMorita-variant. . . . . . . . . . . . . . . 29
OtherAldolandAldol-typeReactions . . . . . . . . . . . . . . . . . . . . . . 29
AllylationandRelatedReactions . . . . . . . . . . . . . . . . . . . . . . . . . 30
TheHorner–Wadsworth–EmmonsReactionandRelatedOlefinations. . . . . . 32
Alkynylations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
StetterReaction,BenzoinCondensationandPinacolCoupling . . . . . . . . . 34
MichaelAdditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
MiscellaneousCondensations . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
OtherAdditionReactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
AdditionofOrganozincs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Arylations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
AdditionofOtherOrganometallics . . . . . . . . . . . . . . . . . . . . . . . . 45
TheWittigReaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
OrganicReactionMechanisms2013,FirstEdition.EditedbyA.C.Knipe.
©2017JohnWiley&Sons,Ltd.Published2017byJohnWiley&Sons,Ltd.
1
2 OrganicReactionMechanisms2013
Hydrocyanation,CyanosilylationandRelatedAdditions . . . . . . . . . . . . . 47
𝛼-AminationsandRelatedReactions . . . . . . . . . . . . . . . . . . . . . . . 48
MiscellaneousAdditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Enolization,ReactionsofEnolatesandRelatedReactions . . . . . . . . . . . . . . 50
𝛼-Halogenation,𝛼-AlkylationandOther𝛼-Substitutions. . . . . . . . . . . . . 51
OxidationandReductionofCarbonylCompounds . . . . . . . . . . . . . . . . . . 51
OxidationofAldehydestoAcids . . . . . . . . . . . . . . . . . . . . . . . . . 51
OxidationofAldehydestoAmides,EstersandRelatedFunctionalGroups . . . 51
Baeyer–VilligerandOtherOxidationReactionsofKetones . . . . . . . . . . . 53
MiscellaneousOxidativeProcesses . . . . . . . . . . . . . . . . . . . . . . . . 53
ReductionReactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
StereoselectiveReductionReactions . . . . . . . . . . . . . . . . . . . . . . . 55
OtherReactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
FormationandReactionsofAcetalsandRelatedSpecies
Equilibriafortheformationofhemiacetalsfromeightisomerichexanalshavebeenmea-
sured in methanol, and compared with the steric environment around the aldehyde.1
Kineticstudieshavealsobeencarriedout,andthesesuggestanearlyTS.
Catalytic asymmetric acetalization of aldehydes has been demonstrated, using large
chiralBINOL-derivedphosphoricacidcatalysts:theseareproposedtogenerateconfined
(cid:2)
chiralmicroenvironments.2 ee
A new enantioselective arylation of enecarbamates (1) has been developed, using a
quinone imine acetal (2) as a functionalized surrogate aromatic, and an axially chiral
BINAP-dicarboxylic acid catalyst.3 The useful 𝛼-amino-𝛽-aryl ether products (3) are (cid:2)ee
formedinupto99%ee,anddesoften>90%,andarefurthertransformableintochiral (cid:2)
de
𝛽-aryl amines and 𝛼-aryl esters. Mechanistically revealing observations include:
(i) trans-enecarbamate switches the sense of asymmetric induction; (ii) the NH in (1)
is critical, presumably for hydrogen bonding to catalyst: the NMe starter fails; and
(iii)crossoverexperimentsfail,implicatinganintramolecularroute.Theproposedfirst
step is a highly stereoselective C–C bond formation followed by aromatization (with
eliminationofR3-OH),thenre-additionofR3-OHtothesidechain.
NR2 NHR2
NHBoc
+ NHBoc
R1 ∗∗
∗∗
OR3
R3O OR3 OR3 R1
(1) (2) (3)
A stable N,N′-diamidocarbene has been used to activate molecules with X–X
homonuclear single bonds (where X=Br, O, S, C).4 Br yields a substituted tetrahy- (cid:2)
2 de
dropyrimidinium salt, benzoyl peroxide yields diamidoacetal product, and various
1ReactionsofAldehydesandKetonesandTheirDerivatives 3
sulfides give the corresponding diamidothioacetals. For X=C, insertion into the
(O)C–C(O) bond of diones was observed, and for cyclopropenone, insertion into the
(O)–C–Cbondoccurred.
meta- and para-Substituted benzaldehyde acetals, X-C H –CH(OBu) , have been
6 4 2
oxidized by N-bromosuccinimide in acetonitrile, to give the corresponding esters
(and alkyl bromide).5 Rates have been measured by the iodometric method, over a
range of temperature. A primary kinetic isotope effect, k /k , is observed, indicating
H D
rate-determining C–H cleavage; a Hammett 𝜎 value of 1⋅4 and activation parameters
aregiven.
KineticsoftheoxidationofarangeofaromaticacetalsbyN-chloronicotinamidehave
beenmeasuredinacetonitrile.6
Thecombinationoftriethylsilyltriflatewitheither2,6-dimethylpyridine(2,6-lutidine)
or 2,4,6-trimethylpyridine (2,4,6-collidine) effectively deprotects acetals of aldehydes
undermild,neutralconditions,whileleavingthoseofketonesunaffected.7Pyridinium-
typesaltintermediatesareproposed.
ThePrinsreactionhasbeenmodelledusingDFT(densityfunctionaltheory),usingan
alkene(RCH=CH ,R=MeorPh),aformaldehydedimer,andaproton-watercluster,
2
H O+(H O) .Bothalkenesfeatureaconcertedpathtogivethe1,3-diols.Anunprece-
3 2 13
dentedhemiacetalintermediate,HO–CH –O–CH(R)–CH CH –OH,wasthenidenti-
2 2 2
fied:itundergoesringclosuretothe1,3-dioxaneproduct.8 Gas-phasePrinsreactionof
formaldehyde dimer with alkene has been studied computationally: it proceeds via a
𝜋-complex(withoutformationofanyintermediate𝜎-complex).9
DFTcalculationshavebeenusedtostudythekineticandthermodynamicparameters
of the oligomerization of formaldehyde in neutral aqueous solution: linear and cyclic
oligomers up to tetramer were examined, and implications for enolization and aldol
reactionswerealsoexamined.10
A series of new naphtha[1,3]oxazino[2,3-𝛼]isoquinolines (4, R1=H, Me, Ph, Ar;
R2=H, OMe) have been prepared from 1-aminomethyl-2-naphthols and 3,4-dihydro-
isoquinolines.11 The predominant diastereomer is trans- (at the 7a- and 15-positions), (cid:2)
de
but a surprising inversion at nitrogen can be observed by NMR (nuclear magnetic
resonance). Computations support ring-opening at the C(7a)-oxygen bond, giving an
iminium-phenolateintermediate.
R2
R1 15 N
7a R2
O
(4)
Forotherreportsofacetals,seethesectiontitled‘MiscellaneousOxidativeProcesses’
later.
4 OrganicReactionMechanisms2013
ReactionsofGlucosides
ProtonaffinitiesandpK shavebeencalculatedforvarioustautomersofd-glucoseandd-
a
fructose,andcomparefavourablywithexperimentalmeasurementsofthepH’sofsugar
solutionsinwater.12
A review surveys the catalysts and mechanistic approaches to alter the reactivity of
hydroxylgroupsincarbohydrates,thusfacilitatingregioselectivemanipulation.13 (cid:2)
de
exo-Glycals[e.g.,(Z)-5and(E)-5]areglycosideswithanexocyclicenolethernextto
theoxygenofthering,areusefulsynthons,andsomehavebiochemicalapplicationsin
theirownright.However,the(E)-isomershavebeeninaccessibletodate.Inatreatment
∘
ofthe(Z)-specieswithstrongbase(aimedatfurtherfunctionalization),t-BuLiat−78 C
surprisingly gave 34% conversion to the (E)-exo-glycal [(E)-5] with no by-products.
A vinyl anionic intermediate was confirmed. Optimum isomerization employed 3mol
∘
LiHDMSatambienttemperaturefor10min(todeprotonate),followedby−100 Cfor
2h,whichfavoursthe(E)-isomer.14
OBn
O
OBn
P
TBSOO TBSOO
Base
O
TBSO P
TBSO
OBn
BnO
TBSO
TBSO
(Z-5) (E-5)
Several formic acid derivatives of a protected glucose have been prepared:
O-perbenzoylated C-(𝛽-d-glucopyranosyl)-formimidate [6, R=C(=NH)OEt], -form-
amidine [R=C(=NH)–NH ], -formamidrazone [R=C(=NH–NHX)–NH , X=H or
2 2
Ts]and-formylchloride(R=COCl).15Designedtoleadto1,2,4-triazolederivativesof
the sugar, they unexpectedly also gave 1,3,4-oxadiazole derivatives. DFT calculations
havebeenusedtoinvestigatethealternativering-formingpathways.
OBz
O
BzO
BzO R
OBz
(6)
Chemo-andregio-selectivefunctionalizationofnon-protectedcarbohydrateshasbeen
developed,allowingselectivethiocarbonylation,acylationandsulfonylationofapartic-
ular carbohydrate in the presence of structurally similar carbohydrates, for example,
anomers.16 For example, sugar anomers (7) can be functionalized in the 6-position in
upto99%yieldand99%𝛽-selectivity,usingMe SnCl ascatalyst.Justswitchingthe
2 2
catalysttoBu SnCl givescomparableyieldsand𝛼-selectivitiesinthe2-position.The
2 2
mechanismsarediscussedintermsofthestericapproachesofthecatalystsatthe1,2-
versus4,6-sites.