Stereochemistry and Organic Reactions: Conformation, Configuration, Stereoelectronic Effects and Asymmetric Synthesis PDF
Preview Stereochemistry and Organic Reactions: Conformation, Configuration, Stereoelectronic Effects and Asymmetric Synthesis
Stereochemistry and Organic Reactions Conformation, Configuration, Stereoelectronic Effects and Asymmetric Synthesis Stereochemistry and Organic Reactions Conformation, Configuration, Stereoelectronic Effects and Asymmetric Synthesis Dipak K. Mandal Formerly ofPresidency College/University Kolkata,India AcademicPressisanimprintofElsevier 125LondonWall,LondonEC2Y5AS,UnitedKingdom 525BStreet,Suite1650,SanDiego,CA92101,UnitedStates 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom Copyright©2021ElsevierInc.Allrightsreserved. Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans, electronicormechanical,includingphotocopying,recording,oranyinformationstorageand retrievalsystem,withoutpermissioninwritingfromthepublisher.Detailsonhowtoseek permission,furtherinformationaboutthePublisher’spermissionspoliciesandourarrangements withorganizationssuchastheCopyrightClearanceCenterandtheCopyrightLicensingAgency,can befoundatourwebsite:www.elsevier.com/permissions. Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightbythe Publisher(otherthanasmaybenotedherein). Notices Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchandexperience broadenourunderstanding,changesinresearchmethods,professionalpractices,ormedical treatmentmaybecomenecessary. Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgeinevaluating andusinganyinformation,methods,compounds,orexperimentsdescribedherein.Inusingsuch informationormethodstheyshouldbemindfuloftheirownsafetyandthesafetyofothers, includingpartiesforwhomtheyhaveaprofessionalresponsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors, assumeanyliabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproducts liability,negligenceorotherwise,orfromanyuseoroperationofanymethods,products, instructions,orideascontainedinthematerialherein. LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress BritishLibraryCataloguing-in-PublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary ISBN978-0-12-824092-2 ForinformationonallAcademicPresspublications visitourwebsiteathttps://www.elsevier.com/books-and-journals Publisher:SusanDennis AcquisitionsEditor:EmilyMcCloskey EditorialProjectManager:AllisonHill ProductionProjectManager:PaulPrasadChandramohan CoverDesigner:VictoriaPearson TypesetbySPiGlobal,India Preface Organicstereochemistryisavastandimportantsubject.Itisanintrinsicpartof allorganicchemistry.Planningandexecutingstereoselectivesynthesistopre- pare single enantiomers as well as single diastereomers is an exhilarating sciencethathasregisteredenormousprogressovertheyears,andstillisinfast development. Understanding of the factors that determine the high levels of three-dimensionalcontrolinorganicsynthesisisanessentialandfundamental topic for all students of organic chemistry. It is not surprising therefore that stereochemistry is covered in every undergraduate, advanced undergraduate andgraduatecourseinorganicchemistry.Itismyinvolvementinteachingthis subjecttoundergraduateandgraduatestudentsformorethan30yearsthathas inspired me to write this book. The purpose of this endeavour is entirely pedagogic,keepinginviewthatourstudentsdesperatelycraveunderstanding, not factual knowledge alone. Understanding requires a ‘feel’ for the set of principles that influence the stereochemistry of organic molecules and their reactions,whichisintheheartofthisbook;thehistoricaldevelopmenthasbeen generally given short shrift. Thebookisprimarilystructuredinthreeparts(PartI–III),andeachpartis factoredintoseveralchapters.AnappendixisincludedinPartIV.PartIdeals with the stereochemistry—conformation and configuration—of acyclic molecules (Chapters 1 and 2) and cyclic molecules (Chapter 3). The stereo- chemistryoforganicreactionsfollowsthereafter.PartIIprovidesanintroduc- tion to perturbation molecular orbital theory for the origin of stereoelectronic effects (Chapter 4) and an introduction to the principles of stereoselectivity and hierarchical levels or generations of asymmetric synthesis (Chapter 5) as a background aid to follow the reaction stereochemistry covered in Part III. Ihopethisuniquestylewouldhelpenhancethepedagogyofthistext.Theste- reochemistryofreactionswithparticularemphasisondiastereoselectivityand asymmetricsynthesisarepresentedinsevenchaptersalongthelinesofmech- anisticclasses.Twoelaboratechapters(Chapters6and7)aredevotedtoionic reactions,themostabundantclass,twoforpericyclicreactions(Chapters8and 9), andone each for transitionmetal-catalysedreactions(Chapter 10),radical reactions(Chapter11) andphotochemical reactions (Chapter 12). The book is distinct from other contemporary textbooks in that it brings a holistic approach by providing, within the limits of space and time, separate chapters on the stereochemistry of reactions of all mechanistic types ranging xvii xviii Preface fromionic,pericyclic,transitionmetal-catalysedtoradicalandphotochemical. Thiswouldundoubtedlyhelprevealtheunifyingprinciplesforstereochemical understandingandprediction.Anotherimportantdifferencebetweenthisbook andothersistheemphasisontheworkingofstereochemistry,specificallyhow todelineatethestereochemistryofproducts.Learningstereochemistryishard work. I have found that students are often not quite comfortable to work stereochemistry for themselves. They need some more help. To address their concerns,Ihavealwaysbeenlookingforinnovativeapproachestostereochem- icalissues.Myeffortshaveproducedsomesimpleandgeneralstereochemical rules/guidelines, some of which have been published in three papers in the Journal of Chemical Education. These published (also some unpublished) rules/mnemonics have been used extensively in the relevant chapters as an aid to draw quickly and correctly the product stereochemistry in organic reactions. Asanelementoflearningandpedagogy,Ihaveprovidedover150problems withinthechapters,reinforcingthemainthemesinthetext.Ihopethatstudents couldtesttheirlearningimmediatelywhilereadingthroughthechapters.These problemsetsshouldbeconsideredanintegralpartofthecourse.Thedetailed answers to the problems with references, wherever necessary, are given in Appendixin Part IV. Ihave provided atotal ofabout 1,400 references topri- mary and review literature, with each chapter containing a reference list at itsend.Thesereferenceswillenablethereaderstogofurtherintothesubject. Theapproachpresentedinthisbookisdistinctandclasstested.Ihavetried tofindaleveltosuiteveryoneinhis/herownwayfromtheundergraduatetothe research level. I hope this book will be of value and interest to the students, teachers and researchers of organic, biological and medicinal chemistry, and alsotoawidercircleofreadersincludingbiologists,pharmacologists,polymer chemistsandchemistsworkinginindustrywhomightwishtohaveanoverview ofthis highly fascinating field of chemistry. Iwouldliketothanktheanonymousreviewersforhelpfulsuggestions.Iam grateful to the editorial members Emily M. McCloskey and Allison Hill, production manager Paul P. Chandramohan, and their colleagues at Elsevier for excellent support and cooperation. Finally, I thank my wife Tapasi and my daughter Sudipta for their continuous support and my son Tirtha for his active help in artwork and referencing. I could not finish without thanking mylittlegranddaughterAdritawhohasprovidedmethenecessaryfillipduring the preparation ofthis book. DipakK. Mandal Kolkata,India Abbreviations Ac acetyl (MeCO) (cid:1) acac acetylacetonato (MeCOCHCOMe ) AIBN azobisisobutyronitrile [Me C(CN)N]N(CN)CMe ] 2 2 Alpine-Borane B-isopinocamphenyl-9-borabicyclo[3.3.1]nonane AQN anthraquinone 9-BBN 9-borabicyclo[3.3.1]nonane BINAL-H binaphthyllithiumaluminium hydride BINAP 2,20-bis(diphenylphosphino)-1,10-binaphthalene BINOL 1,10-bi-2-naphthol Bn benzyl (PhCH ) 2 Boc tertiary-butoxycarbonyl (Me COC]O) 3 box bis-oxazoline bpy 2,20-bipyridine Bs brosylor p-bromobenzenesulphonyl (4-BrC H SO ) 6 4 2 Bu butyl [Me(CH ) ] 2 3 i-Bu isobutyl(Me CHCH ) 2 2 s-Bu secondary-butyl [MeCH C(Me)H] 2 t-Bu tertiary-butyl(Me C) 3 Bz benzoyl(PhCO) CAN cerium(IV) ammoniumnitrate [Ce(NH ) (NO ) ] 4 2 3 6 Cbz benzyloxycarbonyl (PhCH OC]O) 2 CD circular dichroism CE Cottoneffect CIR chiral inducingreagent cod 1,5-cyclooctadiene mCPBA meta-chloroperbenzoic acid (3-ClC H CO H) 6 4 3 CSP chiral stationary phase Cy cyclohexyl (C H ) 6 11 DAIB 3-exo-(dimethylamino)isoborneol dba trans,trans-dibenzylideneacetone [(PhCH]CH) CO] 2 de diastereomeric excess DET diethyl tartrate DHQ dihydroquinine DHQD dihydroquinidine DIBAL-H diisobutylaluminium hydride (i-Bu AlH) 2 DIP-Cl diisopinocamphenylboronchloride(Ipc BCl) 2 xix xx Abbreviations DIPT diisopropyl tartrate DMAD dimethylacetylenedicarboxylate (MeO CC^CCO Me) 2 2 DME 1,2-dimethoxyethane (MeOCH CH OMe) 2 2 DMF N,N-dimethylformamide (Me NCH¼O) 2 DMSO dimethylsulphoxide (Me S]O) 2 dr diastereomer ratio DTBP 2,6-di-t-butylpyridine 2 e electron ee enantiomeric excess ESR electronspin resonance Et ethyl(MeCH ) 2 FMO frontier molecular orbital fod 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionate 1G/2G/3G/4G first/second/third/fourthgeneration gb gauche-butane GC gas chromatography HOMO highest occupied molecular orbital HMPA hexamethylphosphoramide [(Me N) P]O] 2 3 HPLC high performance liquid chromatography IND N-carboxy-indoline IR infrared ISC intersystem crossing Ipc BH diisopinocamphenylborane 2 Ipc BOTf diisopinocamphenylborontriflate 2 KHMDS potassium hexamethyldisilazide [(Me Si) NK] 3 2 LCAO linear combinationof atomic orbitals Lcp left circularly polarized LDA lithiumdiisopropylamide (i-Pr NLi) 2 L-DOPA (S)-30,40-dihydroxyphenylalanine LiHMDS lithiumhexamethyldisilazide[(Me Si) NLi] 3 2 LiTMP lithiumtetramethylpiperidide L-Selectride lithiumtri(sec-butyl)borohydride [Li(s-Bu) BH] 3 LUMO lowest unoccupied molecular orbital 2,6-Lutidine 2,6-dimethylpyridine Me methyl (CH ) 3 Meerwein’s trimethyloxonium tetrafluoroborate (Me O+BF (cid:1)) 3 4 salt Ms mesylormethanesulphonyl (MeSO ) 2 NAD+ nicotinamide adeninedinucleotide NADH nicotinamideadeninedinucleotidehydride(reducedformof NAD+) NaHMDS sodiumhexamethyldisilazide [(Me Si) NNa] 3 2 NBS N-bromosuccinimide NGP neighbouring-group participation Abbreviations xxi NMO N-methylmorpholine-N-oxide NMR nuclear magnetic resonance op optical purity ORD optical rotatorydispersion Oxone potassium peroxymonosulphate (2KHSO (cid:3)KHSO (cid:3)K SO ) 5 4 2 4 Ph phenyl (C H ) 6 5 PHAL phthalazine PHOX phosphinooxazoline PMP 1,2,2,6,6-pentamethylpiperidine PPTS pyridinium p-toluenesulphonate Pr propyl [Me(CH ) ] 2 2 i-Pr isopropyl (Me CH) 2 2-Py 2-pyridinyl QP quinine hypophosphite QDP quinidine hypophosphite RAMP (R)-1-amino-2-(methoxymethyl)pyrrolidine Red-Al sodiumbis(2-methoxyethoxy)aluminiumhydride [NaAlH (OCH CH OMe) ] 2 2 2 2 Rcp right circularly polarized r.t. room temperature SAEP (S)-1-amino-2-(1-ethyl-1-methoxypropyl)pyrrolidine SAMP (S)-1-amino-2-(methoxymethyl)pyrrolidine SET single electron transfer SOMO singlyoccupied molecular orbital TADDOLs α,α,α0,α0-tetraaryl-1,3-dioxolane-4,5-dimethanols TAPA α-(2,4,5,7-tetranitro-9-fluorenylideneaminooxy) propionic acid TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl TBDMS tertiary-butyldimethylsilyl (t-BuMe Si) 2 TBDPS tertiary-butyldiphenylsilyl (t-BuPh Si) 2 Tf triflyl or trifluoromethanesulphonyl (CF SO ) 3 2 TFA trifluoroaceticacid (CF CO H) 3 2 TFAE 2,2,2-trifluoro-1-(9-anthryl)-ethanol 2 (cid:1) TfO triflate(CF SO ) 3 3 THF tetrahydrofuran TIPS triisopropylsilyl (i-Pr Si) 3 TLC thin layer chromatography TMEDA N,N,N0,N0-tetramethylethylenediamine[Me N(CH ) NMe ] 2 2 2 2 TMS trimethylsilyl (Me Si) 3 TOT tri-o-thymotide Ts tosylorp-toluenesulphonyl(4-MeC H SO ) 6 4 2 TS transition structure UV ultraviolet Part I Stereochemistry of organic molecules Amoleculeisamicroscopicgroupingofatomslinkedtogetherbybonds,andits structureisaconceptatthemolecularlevel,whereasaphysicalpropertyrefers toanassemblyofmoleculesorcompoundatthemacroscopiclevel.PartIcom- prisesthreechapters(Chapters1–3)whichdealwiththeconceptsofsymmetry, chirality, conformation, configuration and topicity in organic molecules, and methods based on physical properties to achieve resolution of racemates and to determineconformation, configuration andenantiomeric composition.
The list of books you might like
