Pericyclic reactions : a mechanistic and problem solving approach PDF
Preview Pericyclic reactions : a mechanistic and problem solving approach
Pericyclic Reactions A Mechanistic and Problem-Solving Approach Sunil Kumar Department of Chemistry F.G.M. Govt. College Haryana, India Vinod Kumar Department of Chemistry Maharishi Markandeshwar University Haryana, India S.P. Singh Department of Chemistry Kurukshetra University, Kurukshetra Haryana, India AMSTERDAMlBOSTONlHEIDELBERGlLONDON NEWYORKlOXFORDlPARISlSANDIEGO SANFRANCISCOlSINGAPORElSYDNEYlTOKYO AcademicPressisanimprintofElsevier AcademicPressisanimprintofElsevier 125LondonWall,LondonEC2Y5AS,UK 525BStreet,Suite 1800,SanDiego,CA 92101-4495,USA 225WymanStreet,Waltham,MA02451,USA TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UK Copyright(cid:1)2016ElsevierInc.Allrightsreserved. Nopartofthispublicationmaybereproduced ortransmittedinanyformorbyany means,electronic ormechanical,includingphotocopying,recording, orany informationstorageandretrievalsystem,withoutpermissioninwritingfromthe publisher.Detailsonhowtoseekpermission,furtherinformationaboutthePublisher’s permissionspolicies andourarrangementswithorganizationssuchastheCopyright Clearance Center andtheCopyrightLicensingAgency,canbefoundatourwebsite: www.elsevier.com/permissions. Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyright bythePublisher(otherthanasmaybenotedherein). Notices Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchand experiencebroadenourunderstanding,changesinresearchmethods,professional practices, ormedicaltreatmentmaybecomenecessary. Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledge inevaluating andusinganyinformation,methods,compounds,orexperiments describedherein.Inusingsuchinformationormethodstheyshouldbemindfuloftheir ownsafetyandthesafetyofothers,includingpartiesforwhomtheyhaveaprofessional responsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,or editors,assumeanyliabilityforanyinjuryand/ordamagetopersonsorpropertyasa matterofproductsliability,negligenceorotherwise,orfromanyuseoroperationof anymethods,products,instructions, orideas containedinthematerialherein. ISBN:978-0-12-803640-2 BritishLibrary CataloguinginPublicationData Acatalogue recordforthisbookisavailablefromtheBritishLibrary LibraryofCongressCataloging-in-Publication Data AcatalogrecordforthisbookisavailablefromtheLibraryofCongress ForInformationonallAcademicpresspublications visitourwebsiteat http://store.elsevier.com/ To Our Families Sunil Kumar Parents Dr. Meenakshi, Ayush, Neerav Vinod Kumar Parents Sushma, Mohit, Vignesh S.P. Singh Pushpa, Sunny, Romy Preeti, Preety Poorva, Uday, Adi, Veer Preface EversincetheappearanceoftheclassicTheConservationofOrbitalSymmetry byWoodwardandHoffmannin1970,therehasbeenasurgeinthepublicationof many books and excellent review articles dealing with this topic. This was natural as after having established mechanisms of ionic and radical reactions, focus had shifted to uncover the mechanisms of the so-called “no-mechanism reactions.” The uncovering of the fact that orbital symmetry is conserved in concerted reactions was a turning point in our understanding of organic re- actions. It is now possible to predict the stereochemistry of such reactions by followingthesimplerulethatstereochemicalconsequencesofreactionsinitiated thermallywillbeoppositetothoseperformedunderphotochemicalconditions. Studyofpericyclicreactions,astheseareknowntoday,isanintegralpartofour understandingoforganicreactionmechanisms. Despitethepresenceofmanyexcellentbooksonthisvibranttopic,therewas anabsenceofabookthatconcentratesprimarilyonaproblem-solvingapproach forunderstandingthistopic.Wehadrealizedduringourteachingcareerthatthe mosteffectivewaytolearnaconceptualtopicisthroughsuchanapproach.This bookiswrittentofillthisimportantgapinthebeliefthatitwouldbehelpfulto students to have problems pertaining to different types of pericyclic reactions compiledtogetherinasinglebook. Thebookopenswithanintroduction(Chapter1),which,besidesproviding background information needed for appreciating different types of pericyclic reactions, outlines simple ways to analyze these reactions using orbital sym- metry correlation diagram, frontier molecular orbital (FMO), and perturbation molecularorbital(PMO)methods.Thischapteralsohasreferencestoimportant publishedreviewsandarticles. Electrocyclic, sigmatropic, and cycloaddition reactions are subsequently describedinChapters2,3,and4,respectively.Chapter5isdevotedtoastudyof cheletropic and 1,3-dipolar cycloaddition reactions as examples of concerted reactions. Many group transfer reactions and elimination reactions, including pyrolyticreactions,areincludedinChapter6.Therearesolvedproblemsineach chapterthataredesignedforstudentstodevelopproficiencythatcanbeacquired only by practice. These problems, about 450, provide sufficient breadth to be adequatelycomprehensive.Solutionstoalltheseproblemsareprovidedineach chapter. Finally, in Chapter 7, we have compiled unworked problems whose xi xii Preface solutionsareprovidedseparatelyintheAppendix.Theaimbehindintroducing theseunsolvedproblemsistoletthestudentsdeveloptheirownskills. Assumingthatastudenthastakencoursesinorganicchemistrythatinclude reaction mechanisms and stereochemistry, the bookis meant to be taught as a one-semestercoursetograduateandseniorundergraduatestudentsmajoringin chemistry.Onehastorememberthatabookdesignedforaone-semestercourse cannot include all the reactions reported in the literature; rather, only repre- sentativeexamplesofeachofvariousreactiontypesaregiven.Ageneralindexis included,whichitishopedwillbeofhelptoreadersinsearchingforthetypesof reactionsrelatedtoaparticularproblem. We hope that our book will be well received by students and teachers. We encourage all those who read and use this book to contact us with any comments,suggestions,orcorrectionsforfutureeditions.Ouremailaddresses are: [email protected], [email protected], and shivpsingh@ rediffmail.com. We thank our reviewers for carefully reading the manuscript and offering valuablesuggestions.Finally,wethanktheeditorialstaffofElsevierforbringing thebooktofruition. July2015 SunilKumar VinodKumar S.P.Singh Chapter 1 Pericyclic Reactions and Molecular Orbital Symmetry Chapter Outline 1.1 ClassificationofPericyclic 1.5 AnalysisofPericyclic Reactions 2 Reactions 13 1.2 MolecularOrbitalsof 1.5.1 OrbitalSymmetry AlkenesandConjugated Correlation Diagram PolyeneSystems 3 Method 13 1.3 MolecularOrbitals 1.5.2 FrontierMolecular ofConjugatedIons OrbitalMethod 15 orRadicals 7 1.5.3 PerturbationMolecular 1.4 SymmetryProperties ofpor OrbitalMethod 17 s-MolecularOrbitals 11 FurtherReading 19 Inorganicchemistry,alargenumberofchemicalreactionscontainingmultiple bond(s) do not involve ionic or free radical intermediates and are remarkably insensitivetothepresenceorabsenceofsolventsandcatalysts.Manyofthese reactionsarecharacterizedbythemakingandbreakingoftwoormorebonds inasingleconcertedstepthroughthecyclictransitionstate,whereinallfirst- order bondingsare changed. Such reactions are namedas pericyclicreactions by Woodward and Hoffmann. The word concerted means reactant bonds are broken and product bonds are formed synchronously, though not necessarily symmetrically without the involvement of an intermediate. Theword pericyclic means the movement of electrons (p-electrons in most cases) in a cyclic manner or around the circle (i.e., peri¼around, cyclic¼circle or ring). They are initiated by either heat (thermal initiation) or light (photo initiation) and are highly stereospecific in nature. The most remarkable observation about these reactions is that, very often, thermal and photo- chemical processes yield products with different stereochemistry. Most of these reactions are equilibrium processes in which direction of equilibrium depends on the enthalpy and entropy of the reacting species. Therefore, in general, three important points that should be considered while studying the PericyclicReactions.http://dx.doi.org/10.1016/B978-0-12-803640-2.00001-4 Copyright©2016ElsevierInc.Allrightsreserved. 1 2 PericyclicReactions pericyclicreactionsare:involvementofp-electrons,typeofactivationenergy required (thermal or light), and stereochemistry of the reaction. There is a close relationship between the mode of energy supplied and stereochemistry for a pericyclic reaction, which can be exemplified by considering the simpler reactions shown in Scheme 1.1. SCHEME1.1 Stereochemicalchangesinpericyclicreactionsunderthermalandphotochemical conditions. When heat energy is supplied to the starting material, then it gives one isomer,whilelightenergyisresponsibleforgeneratingtheotherisomerfrom the same starting material. 1.1 CLASSIFICATION OF PERICYCLIC REACTIONS Pericyclicreactionsare mainlyclassified intothe four mostcommon types of reactions as depicted in Scheme 1.2. SCHEME1.2 Commontypesofpericyclicreactions. In an electrocyclic reaction, a cyclic system (ring closure) is formed through the formation of a s-bond from an open-chain conjugated polyene system at the cost of a multiple bond and vice versa (ring opening). These reactions areunimolecular innature astherate ofreactions dependsuponthe PericyclicReactionsandMolecularOrbitalSymmetry Chapter j1 3 presence of one type of reactant species. Such reactions are reversible in nature, but the direction of the reaction is mainly controlled by thermody- namics. Most of the electrocyclic reactions are related toring closingprocess instead of ring opening due to an interaction between the terminal carbon atoms forming a s-bond (more stable) at the cost of a p-bond. Sigmatropicrearrangementsaretheunimolecularisomerizationreactions inwhichas-bondmovesfromonepositiontoanotheroveranunsaturatedsystem. Insuchreactions,rearrangementofthep-bondstakesplacetoaccommodatethe news-bond,butthetotalnumberofp-bondsremainsthesame. Incycloadditionreactions,twoormorecomponentscontainingp-electrons come together to form the cyclic system(s) through the formation of two or morenew s-bondsat the costofoverall two ormore p-bonds, respectively, at least one from each component. Amongst the pericyclic reactions, cycloaddi- tions are known as the most abundant, featureful, and valuable class of the chemical reactions. The reactions are known as intramolecular when cycload- dition occurs within the same molecule. The reversal of cycloaddition in the same manner is known as cycloreversion. There are some cycloaddition reactionsthatproceedthroughthestepwiseionicorfreeradicalmechanismand thus are not considered as pericyclic reactions. These reactions are further extended to cheletropic and 1,3-dipolar reactions, which shall be discussed in detail in Chapter 5. Group transfer reactions involve the transfer of one or more atoms or groups from one component to another in a concerted manner. In these reactions,twocomponentsjointogethertoformasinglemoleculethroughthe formation of a s-bond. Itisveryimportanttonotethatinstudyingthepericyclicreactions,thecurved arrowscanbedrawninclockwiseoranticlockwisedirection(Scheme1.3).The directionofarrowsdoesnotindicatetheflowofelectronsfromonecomponentor sitetoanotherasinthecaseofionicreactions;rather,itindicateswheretodraw thenewbonds. SCHEME 1.3 Clockwise and anticlockwise direction of the curved arrows in pericyclic reactions. 1.2 MOLECULAR ORBITALS OF ALKENES AND CONJUGATED POLYENE SYSTEMS In order to understand and explain the results of the various pericyclic re- actions on the basis of different theoretical models, a basic understanding of the molecular orbitals of the molecules, particularly those of alkenes and conjugated polyene systems and their symmetry properties, is required. 4 PericyclicReactions According to the molecular orbital theory, molecular orbitals (MOs) are formed by the linear combination of atomic orbitals (LCAO) and then filled by the electron pairs. In LCAO when two atomic orbitals of equivalent energy interact, they always yield two molecular orbitals, a bonding and a corresponding antibonding orbital. The bonding orbital possesses lower energyandmorestabilitywhileantibondingpossesseshigherenergyandless stability as compared to an isolated atomic orbital. Let us consider the simplest example of H molecule formed by the combination of 1s atomic 2 orbitals (Figure 1.1). nodal plane Eσ* (σ*) antibonding E 1s 1s Eσ H H (σ) bonding molecular orbitals FIGURE1.1 FormationofmolecularorbitalsinthecaseofanH2molecule. Thebondingmolecularorbitalisaresultofpositive(constructive)overlap, andhenceelectrondensityliesintheregionbetweentwonuclei.However,an antibonding molecular orbital is formed as a result of negative (destructive) overlap and, therefore, exhibits a nodal plane in the region between the two nuclei. The bonding and antibonding molecular orbitals exhibit unequal splitting pattern with respect to the atomic orbitals because a fully filled molecular orbital has higher energy due to interelectronic repulsion. We now consider molecular orbital theory with reference to the simplest p-molecular system, ethene. As already discussed, the number of molecular orbitals formed is always equal to the number of atomic orbitals combining together. Similarly, in the case of an ethene molecule, sideways interaction betweenp-orbitalsofthetwoindividualcarbonatomsresultsintheformation of the new p bonding and p* antibonding molecular orbitals that differ in energy (Figure 1.2). In the bonding orbital of ethene, there is a constructive overlap of two similar lobes of p-orbitals in the bonding region between the nuclei. However, in the case of an antibonding orbital, there is destructive overlapoftwooppositelobesinthebondingregion.Eachp-orbitalconsistsof two lobes with opposite phases of the wave function. We ignore s-bond skeleton in this treatment as sigma molecular orbitals remain unaffected during the course of a pericyclic reaction. The conjugated polyenes constitute an important class of organic compounds exhibiting a variety of pericyclic reactions. On the basis of the PericyclicReactionsandMolecularOrbitalSymmetry Chapter j1 5 node nodal plane • π* antibonding node • nodal plane E p-orbital π p-orbital p-orbital bonding Ethene FIGURE1.2 Formationoftwomolecularorbitals(pandp*)ofethene. number of p-electrons, such compounds are classified into two categories bearing4nor(4nþ2)p-electronsystems.Inordertoconstructthemolecular orbitals for such polyene systems, let us consider buta-1,3-diene as the simplest example. Inthemoleculeofbuta-1,3-diene,therearefourp-orbitalslocatedonfour adjacentcarbonatomsandhencethisgeneratesfournewp-molecularorbitals on overlapping. The way to get these new p-molecular orbitals is the linear combination of two p-molecular orbitals of ethene according to the perturbationmolecularorbital(PMO)theory.Likethecombinationofatomic orbitals,overlappingofthebonding(sorp)orantibondingmolecularorbitals (s* or p*) of the reactants (here, ethene) results in the formation of the new molecular orbitals that are designated as J , J , etc. in the product (here, 1 2 buta-1,3-diene). AccordingtoPMOtheory,linearcombinationalwaystakesplacebetween the two orbitals(two molecularorbitals ortwo atomic orbitals, or oneatomic andonemolecularorbital)havingminimumenergydifference.Thus,herewe need to consider pep and p*ep* interactions (constructive or destructive) instead of interactions between p and p* orbitals (Figure 1.3). In buta- 1,3-diene, 4p-electrons are accommodated in the first two p-molecular or- bitals, and the remaining two higher energy p-molecular orbitals will remain unoccupied in the ground state of the molecule. The lowest energy orbital (represented as wave function J ) of buta- 1 1,3-dienedoesnothaveanynodeandisthemoststableduetothepresenceof three bonding interactions. However, the second molecular orbital J 2 possessesonenode,twobondingandoneantibondinginteractions,andwould be less stable than J . The J has two nodes and one bonding interaction. 1 3 Due to the two antibonding interactions, J possesses overall antibonding 3 characterandthusenergyofthisorbitalismorethantheenergyofJ .TheJ 2 4 orbital is formed by the interaction between p* and p* of two ethene mole- cules. It bears three nodes and the highest energy. Similarly,inthecaseoflongerconjugatedsystemslikeahexa-1,3,5-triene system, there are six p-orbitals on six adjacent carbon atoms, which can
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