Structure, Bonding and Reactivity of Heterocyclic Compounds

199 Pages·2014·5.93 MB·English

by  Frank De Proft, Paul Geerlings (eds.)

Topics in Heterocyclic Chemistry 38
Series Editors: B.U.W. Maes · J. Cossy · S. Polanc
Frank De Proft
Paul Geerlings Editors
Structure, Bonding
and Reactivity
of Heterocyclic
Compounds
38
Topics in Heterocyclic Chemistry
SeriesEditors:
Bert U.W. Maes, Antwerpen, Belgium
Janine Cossy, Paris, France
Slovenko Polanc, Ljubljana, Slovenia
Editorial Board:
D. Enders, Aachen, Germany
S.V. Ley, Cambridge, UK
G. Mehta, Bangalore, India
K.C. Nicolaou, La Jolla, CA, USA
R. Noyori, Hirosawa, Japan
L.E. Overmann, Irvine, CA, USA
A. Padwa, Atlanta, GA, USA
Aims and Scope
The series Topics in Heterocyclic Chemistry presents critical reviews on present
andfuturetrendsintheresearchofheterocycliccompounds.Overallthescopeisto
covertopicsdealingwithallareaswithinheterocyclicchemistry,bothexperimental
andtheoretical,ofinteresttothegeneralheterocyclicchemistrycommunity.
The series consists of topic related volumes edited by renowned editors with
contributionsofexpertsinthefield.
More information about this series at
http://www.springer.com/series/7081
Frank De Proft • Paul Geerlings
Editors
Structure, Bonding and
Reactivity of Heterocyclic
Compounds
With contributions by
R. Broer • J. Cadet • S. Catak • N. De Kimpe • F. De Proft •
M. D’hooghe • F. Feixas • P. Geerlings • H. Goossens •
A. Grand • M.Z. Griffiths • R.W.A. Havenith •
D. Hertsen • V.T.T. Huong • N. Jorge • L. Joubert •
V. Labet • E. Matito • K. Mollet • C. Morell •
M.T. Nguyen • J. Poater • P.L.A. Popelier •
Z. Rashid • M. Sola` • O.A. Syzgantseva • T.B. Tai •
V. Tognetti • J.H. van Lenthe • V. Van Speybroeck •
M. Waroquier
Editors
FrankDeProft
PaulGeerlings
ResearchgroupofGeneralChemistry
VrijeUniversiteitBrussel(VUB)
Brussels
Belgium
ISSN1861-9282 ISSN1861-9290(electronic)
ISBN978-3-642-45148-5 ISBN978-3-642-45149-2(eBook)
DOI10.1007/978-3-642-45149-2
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2014953968
#Springer-VerlagBerlinHeidelberg2014
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Preface
This volume of “Topics in Heterocyclic Chemistry” focuses on the aspects of
structure, bonding and reactivity of heterocyclic systems. It aims at presenting a
series of different state-of-the-art methods and concepts available in quantum
mechanics and theoretical chemistry to probe these different important aspects of
heterocycliccompounds.
Inquantumchemistry,quantummechanicsisappliedtoproblemsinchemistry.
An important goal in this field, among others, is to accurately solve the time-
independent Schro¨dinger equation for molecular systems, yielding the different
energystatesofthesystemandtheaccompanyingwavefunctions,fromwhichall
propertiescanbeobtained.Unfortunately,thisequationcanonlybesolvedexactly
for one-electron systems; for many-electron systems, approximations have to be
made. In recent decades, powerful and accurate methods have been developed.
Accompanied by the ever-increasing power of computers and the availability of
dedicated specialized software, accurate calculations of different properties of
compounds of ever-increasing size can now be performed. These properties
include, among others, molecular structures and energetics, such as reaction
energies and activation barriers, both of importance to describe thermodynamic
andkineticaspectsofachemicalreaction.Thisoftenrequirestheexplicittreatment
oftheeffectofthesolvent,whichcanplayacrucialroleindeterminingchemical
reactivity.Often,useismadeofdensityfunctionaltheorymethods,which,instead
ofthewavefunction,adopttheelectrondensityasthebasicquantitytodescribeall
atomicandmolecularproperties.Anotherimportantaspectofquantumchemistryis
thatitservesasasourcefortheevaluationandcomputationofconcepts.Chemistry
hastraditionallyusedandcontinuestouseaseriesofpowerfulconceptsinorderto
explain chemical behaviour. These concepts are not only invoked to provide
rationalization,buttheyarealsoappliedinapredictivemanner.Alreadyfromthe
early days of quantum mechanics, a lot of attention has been devoted to the
computationofthesechemicalconcepts,whichareoftennotexperimentallymea-
surable or, in quantum mechanical terms, correspond to non-observables. In this
volume, attention will also be devoted to the use of a selected number of these
conceptstorationalizethebondingandreactivityofheterocycliccompounds.
v
vi Preface
In the first chapter in this volume, Van Speybroeck et al. show how computa-
tionalchemistryandmolecularmodelling,insynergywithexperiment,canplayan
important role in the elucidation of various aspects related to the reactivity of
aziridiniumions,importantintermediatesinthesynthesisoffunctionalizedamines
and other nitrogen-containing organic compounds. This chapter focuses on the
computation of ring strain and the role of the solvent, N- and C-substituents and
nucleophile on the kinetics (through activation-free energies) of regio- and
stereocontrolled ring opening of the aziridinium ions. Density functional theory-
based reactivity descriptors are introduced to probe the regio- and stereochemical
preferencesinthering-openingreaction.Thesereactivitydescriptorsarediscussed
inmoredetailbyMorelletal.inthesubsequentchapter,payingattention,among
others, to the intricacies of the less frequently used selectivity descriptors for
excitedstates.Inaddition,theseauthorsdescribetheirapplication,inparticularof
theso-calleddualdescriptor,toaveryimportantseriesofheterocyclicringsystems,
DNA bases. It is investigated how both global and local DFT-based reactivity
indices can provide insights into the occurrence and formation mechanisms of
DNAlesions.
Theroleoftheelectrondensityasacentralquantityindensityfunctionaltheory
isalreadyemphasizedintheabovechapters.However,theanalysisofthetopology
ofthisfunction has been proven toalso give important insights into the structure,
bondingandreactivity.ThisapproachisthecentraltopicinthechapterofPopelier
etal.,focusingindetailonthecharacterizationoffive-memberedheterocyclicring
systemsthroughthetheoryofquantumchemicaltopology(QCT).Afterashorttour
d’horizonofQCT,theauthorsshowthatringatompropertiescanbeobtainedfrom
theringcriticalpoint(RCP)properties,andintheirquestfordeterminingaring’s
net charge, they introduce the concept of ring characteristic orthogonality, with
different characteristics of a ring affecting the ring’s properties orthogonally. The
RCP and ring atom properties of the model are finally tested against the IGPD
inhibitormolecules.
Themajorityofquantumchemicalcalculationsnowadaysareperformedwithin
the molecular orbital (MO) framework. In this approach, molecular orbitals are
constructed as a linear combination of (atom-centred) atomic orbitals. These
molecular orbitals on the other hand are delocalized over the whole molecule
and, thus, provide no straightforward connection to the Lewis picture of bonding
often used by chemists. Valence bond (VB) theory was introduced almost at the
same time as the MO approach around 1930, but received much less attention in
subsequentdecadesduetoitscomputationalintricacies.Inrecentyears,itregained
interest as described by Havenith et al. in the chapter “Valence Bond Theory in
Heterocyclic Chemistry,” providing an alternative method that more closely
connectstotheconceptofamoleculebeingatomsconnectedbybondsconsisting
of electron pairs. The method is subsequently discussed within the context of
heterocyclic rings, leading to the conclusion that VB is a strong tool in the
interpretation of the electronic structure in terms of classical chemical concepts
such as bond bending, hyperconjugation and aromaticity. The last concept, of
ubiquitous importance when studying unsaturated rings, is further elaborated on
Preface vii
inthefinaltwochaptersofthevolumeinthecaseofheterocyclicringsystems.As
statedanddiscussedindetailinthecontributionofSolaetal.,thisconcept,related
tothecyclicdelocalizationofelectrons,cannotbedefinedwithoutambiguity,andit
isoftenindirectly“measured”onthebasisofitsrepercussiononvariousproperties
ofthemolecule.Theseauthorsdiscussthisconceptforbothorganicandinorganic
monocycleswithspecialemphasisonthemeasuresbasedonelectrondelocalization
propertiesofaromaticrings.
Inthe final chapter,Nguyenet al. focus on the aromaticityof polyheterocyclic
systemscontainingsulphurandtheirderivatives,suchasannulatedoligothiophenes
(sulflower)andtheirO,Se,PH,PFandNHanalogues.Inaddition,thischapteralso
discusses the use of the electron localization function (ELF) to probe aromaticity
and to gain insight into bonding in these particular systems. The concept of disk
aromaticity is thereby proposed to be an effective measure of the aromaticity of
polyheterocycles.
Insummary,thevolumepresentsabroadoverviewofconceptsandthewaythey
canbequantifiedbystate-of-the-arttechniquestostudythestructure,bondingand
reactivityofheterocycliccompounds.
Brussels,Belgium FrankDeProft
PaulGeerlings
ThiSisaFMBlankPage
Contents
ReactivityofAziridiniumSaltsinDifferentSolventsUnraveled
byaCombinedTheoreticalandExperimentalApproach. . . . . . . . . . . 1
HanneloreGoossens,DietmarHertsen,KarenMollet,SaronCatak,
MatthiasD’hooghe,FrankDeProft,PaulGeerlings,NorbertDeKimpe,
MichelWaroquier,andVeroniqueVanSpeybroeck
CharacterizationoftheChemicalReactivityandSelectivity
ofDNABasesThroughtheUseofDFT-BasedDescriptors. . . . . . . . . . 35
VanessaLabet,ChristopheMorell,VincentTognetti,OlgaA.Syzgantseva,
LaurentJoubert,NellyJorge,Andre´ Grand,andJeanCadet
CharacterisingHeterocyclicRingsThroughQuantum
ChemicalTopology. .. . . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . . .. 71
MarkZ.GriffithsandPaulL.A.Popelier
ValenceBondTheoryinHeterocyclicChemistry. . . . . . . . . . . . . . . . . . 103
ZahidRashid,RiaBroer,JoopH.vanLenthe,andRemcoW.A.Havenith
AromaticityofOrganicandInorganicHeterocycles. . . . . . . . . . . . . . . 129
FerranFeixas,JordiPoater,EduardMatito,andMiquelSola`
ChemicalBondingandAromaticityinPoly-heterocyclic
Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
TruongBaTai,VuThiThuHuong,andMinhThoNguyen
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
ix