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Pericyclic chemistry.

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Sanjeeb Acharya
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1K views188 pages

SSR Book

Pericyclic chemistry.

Uploaded by

Sanjeeb Acharya
Copyright
© © All Rights Reserved
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S. Sankararaman Pericyclic Reactions — A Textbook Reactions, Applications and Theory With a Foreword by-Roald Hoffmann ConTENTS: Foreword Preface 1 MOLECULAR ORBITALS AND THEIR SYMMETRY 1.1 Molecular Orbitals 1.2 Molecular Orbitals of Conjugated Polyene Systems 1.3 Symmetry Elements and Symmetry Operations 1.4 Definition and Classification of Perieyclic Reactions 14.1 Electrocyelie Ring Closure and Ring Opening Reactions 142 Cycloaddition and Cycloreversion Reactions 143. Sigmatropic Rearrangements 1.44 Chelotropie Reactions 145 Group Transfer Reactions 1.5 Methods of Analyzing Pericyclic Reactions 1.5.1 Orbital Symmetry Correlation Method 1.52 Frontier Orbital Method 1.53 Transition State Aromaticity Method References 2 ELECTROCYCLIC REACTIONS L2A” Definition of Electrocyelic Reactions \227 Classification of Electroeyetic Reactions 23 Stereochemistry of Flectrocyelie Reactions ‘Woodward-Hoffimann Rules for Electrocyclic Reactions usa 2.4.1 Frontier Orbital Method of Analysis of Electrocyclic Reactions 24.2 Orbital Symmetry Correlation Method for the Electrocyclic Reactions 243 Transition State Aromaticity Method 2.5 Blectrocyclic Reactions Exemplified 2.5.1 Three-membered Ring Systems 25.2 Four-membered Ring Systems Perit Ration. Sanarran pyre © 2s WILEY-VCH Weg Gb & Co KGaA, Welnsin ee og xu 9 9 19 0 a4 a 3 2 2 a ‘YAM Contents 1353. Fivememberod Ring Systems ‘2s Sivmembered Ring System 255. Sevenmembered Ring Systems 156 Eightmenbered Ring Systems 1157 Miselancous Higher Order Systems References 4 CYCLOADDITION REACTIONS bain 32 Clasifieaton 3a Stenodtemisiy of Cyeoadton Rections 2 WondanoTinaa Rls fo Cysoadton Resins S41 Fete Onis Method 542. Orial Conlon Method 343 Tension Sat Aromatiy Method 35 thswaions of Cylon Reasons si x+2e] Cleans “52 Photochemical 2x +25} Cyloaditions 4353 Themal 2x, +2n Cylosdions 3.54) IrunolcularCysloadition Reactions of Ketenes e <= Figure 2 Formation of C-H bond by the overlap of «sp? orbital of carbon anda Is orbital of hydrogen. CC sigma bond: The C-C sigma bond is formed by the interaction of either the p otbital or one of the hybridized orbitals on each of the carbon atoms, The interaction Figure 1.3, and leads to a takes place along the axis of the orbit, as shown i bonding and an antibonding sigma moleeular orbital. (C-Cx bond: A C-C rbond is formed by the interaction ofthe p orbital on each ofthe carbon atoms, not along the axis of the orbital (p.), but laterally, as shown in Figure is mode generates a x bonding and a x* 1.4, The interaction of p orbitals in antibonding MO. Pitorally these orbitals can be represented either in the delocalized form or inthe localized form. Throughout the text we shall be using the later format, much easier to represent. The nodal points are also clearly seen (Figure 1.4). ‘In summary, itis important to remember the following points about the LCAO method 1.1 Molecular Orbitals S~ 1 Inger atic oiled to odig moll ets nd tion ifthe overlap integral is positive, ie. $>0. x 2. Insaston of 2 amie ia nds othe formation of 2x Mos, tnd and m antibonding orbitals. i . 3. The boing MO more sate han te owe enya fe suing sonic bias CB@CeO cox Ses ’ COO. i o Figure 1.3. Formation of C-C sigma bond MOs by the overlap ofp, orbitals of carbon. T delocalized representation Figure 14 The x molecular orbitals of ethylene formed by the interaction of carbon prorbitals, and Theit Symmetry 41 Molecular Ot “4, Theanitvning MO ies sable han the hiher energy ota he sain omic cet oe Boing cea it stabilized fet than hearing ial destabilize. 112 Melwaler Orbital of Conjugated Poly ene System: ne systems tn ery ations 6 oflen enounter reactions of conjugated RSD Depending upon the umber lassifid as Amor 402 lect systems Molecular orbitals of po prema Properis eas to ientify by ftlowing some st vue know bow 10 construct the MOs of jecatdiene on eonrtstoy ing closure wil ve IPE cis 3 4imethyleyelobutene aes he BE: or the 22 isomers on conrlton fing os will give rans-3.4- crigelbiene. Sima, the Z-bexa2-dien 08 sooo ring closure sit ie rans-34-dimetykeytobutee wes the EE and 2.zZisomers will give 1 3 4dimethyleyelobutene (Eqs. 4 and 5) twist ithe the csisomer of th clic reactions tell us whether a system “The Woodward-Hofimann rules for electoey wal undergo the convitory ot the dirtatory mode of reaction under @ BIS wrnton. The mde is citated hy the numberof electrons involved inthe reaction, amely, an or 4n42 system of elesitons and also by whether the reaction is thermally or photochemically activated. 4 24 Woodward Hoffmann Rules fr Electrocyli Reactions 21 Wie, SP cqncttey yon, een om bad CH OH tng a e ze eof SN ceive 47 eaten ora OR Ga zz os 4 ot, : we, ‘i Saeco Sat "yet = rare a ce - ‘Scheme 2.2 Stereochemistry of ring opening/ring closing electrocyclic reactions. 24 Woodward-Hoffmann Rules for Electrocycic Reactions: “The Woodward-Hoffmann rues for the clecrocysic reations ean be derived using any one of the methods discussed in Chapter 1, Section 1.5. Let us consider the ‘method, the orbital symmetry correlation method, and the transition frontier orbit state aromatiity method in the following sections. 2.4. Frontier Orbital Method of Analysis of Electrocyclic Reactions: ‘The molecular system undergoing the clecrocycic reaction is first identified as ar electron or « 442 electron system. Then the HOMO of the system is chosen and analyzed for the two modes of reaction namely the conrotatory mode and the disrottory mode, Based on whether the interaction of the orbitals on the terminal carbon atoms corresponds to bonding or antibonding interaction the allowedness of the disallowedness ofthe reaction is predicted. Let us consider the elestoeyelic ring closure of butadiene to eyelobutene and hexatriene to eyclohexadiene, These belong, to dn electron and 4n*2 electron systems as they involve 4x and 6x electrons, 40 with one node and the HOMO of respectively, The HOMO of butadiene isthe hhexatiene is the ry MO with two nodes in the ground state (Figure 21) ) oor BO RPO bonding fl ong iracton = noMoetiwasere Bre tS Bp cet anibonding tba ,nowodt basset ieets Nit ex ~ So bong interacton sy nouotnerarene foes Wier anivonding interaction HOMO ot exatiene inte TS igure 2.1 Frontier orbital the ground state electronic configuration. ration for 4n and 41r42 electrocyclic reaction From Figure 2.1 itis lear that inthe case of butadiene cyclization to eyclobutene the conrottory mode of rng closure leads to bonding interaction of the terminal carbon atoms in the HOMO of the electronic ground state and hence, is allowed unde: thermal conditions, whereas the altemative mode of ring closure, namely the disrotation, leads to antibonding interaction ofthe terminal carbons in the TS. Hence it is thermally forbidden or disallowed. In general. for a 4n electron svstem the antboncing orbits! 242 Onbital Symmetry Creation Method fot Hetracyeic Resctions. 23 omtotatory male of ting closure and ving opening is chermally allowed whereas the Aisoatory mode of rng closure and ing opening i hermally dsalowed tothe ease ‘of the hexatriene system the distotstory mode of ring clnure fads to bonding Interaction in the HOMO of the electronic ground state in the TS whereas the ‘conrotatory mode of rng lowe leads to antibonding interaction inthe TS. Therefore in the ease of the her ene system, or in general in 4n*? electom systems, the Jisroatory mode of ring closure and fing opening is thermally allowed whereas the conrotatory move of ting opening and ring closure is thermally disallowed. If we consider the ex ted state of butadiene and hetatrene (photochemical concn) the HOMO of the former ist) and that ofthe later is x (Figure 22) Inthe excited sate the conrotatory mode of ring closure and ring opening of the butaiene of any tn eleletzon system is forbidden. It isthe disotatory mode of reaction that leads 12 ‘bonding interaction in the TS and hence is photochemically allowed. Similaly i the hhexatriene cas, in the excited sate the conrotatory mode of easton i allowed and hence under photochemical conditions the hexariene system of any 4 lection system will undergo a conrotatory ring closure / ring opening reaction The ame conclusions ean be drawn using the orbital symmetry correlation method 24.2 Orbital Symmetry Correlation Method for the Electrocyelic Reactions: In this method itis necessary to fist entity the symmetry element that is maintained ‘throughout the reaction in the conrotatory and disrottory modes of reaction. Using that symmetry element the MO are classified as either symmetric or antisymmetic. (Once the symmetry properties of the MOs of the stating material and the pro‘st are identified then is easy to comlate and prodict whether a given process will occur in the ground state or inthe excited state Let us first consider the conrotatory and disrotatory modes of reaction, From Figue 2.3 it is evident that in the conrotatory mode it is the C: axis of symmetry that is pres {all through the reaction whereas inthe disrotatory mode itis the mirror plane () that is maintained throughout the course of the reastion. Therefore we need to use the Cz axis of symmetry while analyzing the eonrotatory mode of the reaction and the tnirror plane for the disrotatory mode of the reaction, Note that both these symmetry elements bisect the newly formed xand or bonds. 242 Electroeyclie Reactions eh Be ORSO nding obi oun eected = ae bonding Poets hipme pe oes antvonding otal wma megane a Sep ‘bonding orbital rouosest pons weteee be a ok Sek arta oa a cayenne Figure 2.2 Frontier orbital interaction for 4 and 4n+2 electrocyelic reactions in the excited state electronic configuration. NO) exrtaton re ea a x) fi) Q— cc S o 6 * : S \ censesaten Ise a 2 o eI Q 13 2 Figure 23 Mdentification of symmetry elements for the conrotatory modes of electrocyclic reactions. freatry and In Figure 24 the x moles rials of aes along with thet metry propery wi spect othe Cy axis of symmety are shown on he et. The male bis of the newly formed a bond and the = boat of sylobten aloe wit hee syne propety wih respect tothe C; axis ym are shown one ight. The moet ctitats of butadiene and eslobuene bering he sie ety ae comet ins hich ar the symmetry comation tins. From the fig itis clear ht hex, MO of butadiene consates withthe x MO ofepelebtene (otha atm wid spect to Cand the xy MO ofthe forms with he @ MO ofthe ater (hth are symm sith rape 9 C9) ly the empty antibonding MOs are correlated While doing the orbital symmetry correlation care is taken not to violate the nom crossing rule, be orbitals of closest energy are correlated ist Bfore a corelation is ‘made with an orbital of higher energy. For example the #2 MO of butadiene can be symmetry correlated to ether theo orbital r the * orbital of eyelobutene, Howeve i ‘vill bea violation ofthe non-srossing rule ithe my of butadiene were o be colt Similarly, the % of butadiene ean be symmetry cotlated nthe * of eyelobutene. only to the # ofeyelobutene and not tothe o* of eyclabutene 26.2 Elestrocyelic Resstions a) , operation Hea LUMO ___ No crossing of HOMO - LUMO gap i electron system for Figure 24. Orbital symmetry correlation diagram for a 4m clectron SY conrotatory electrocyclic reaction. “The orbital symmetry corelaton diagram in Figure 2.4 shows that the bonding of butadiene ae symmetry coneated withthe bonding MOs of eyelobutene and ss corresponding antibonding MOs of butadiene are symmetry correlated with ‘2 antibonding MOs of eyclabutene in the ground slate electronic configuration. implies that the conrotatry ring closure / opening reaction of butadiene / eyelobutew” 's symmetry allowed in te ground state electronic configuration, which means that the reaction is thermally allowed, In Figure 2.5 the orbital symmetry correlation diagram is, shown for the disrotatory mode ofthe ring closure / opening reaction. ‘ymmety cole only in the excited sate which implies hat the daraeny es ‘caction is allowed only under photochemical conditions. Since the photochemical ‘sastion takes place from the electronic excited wate ofthe molecule this conelation a Possible only under photochemical cond ns. In Figure 26 and 2.7 the oftital

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