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1、D.A.EvansAnIntroductiontoFrontierMolecularOrbitalTheory-1Chem206■ProblemsoftheDayhttp://www.courses.fas.harvard.edu/~chem206/ThemoleculeillustratedbelowcanreactthrougheitherPathAorPathBtoformsalt1orsalt2.Inbothinstancesthecarbonyloxygenfunctionsasthehttp://evans.harvard.edu/problems/nuc
2、leophileinanintramolecularalkylation.Whatisthepreferredreactionpathforthetransformationinquestion?Chemistry206OPathA+O1BrNOBr–AdvancedOrganicChemistryBrBrHNOHOPathB2+BrLectureNumber1NOBr–HThisisa"thought"questionposedtomebyProf.DuiloArigoniattheETHinIntroductiontoFMOTheoryZuerichsomeyea
3、rsago■GeneralBondingConsiderations■TheH2MoleculeRevisited(Again!)■Donor&AcceptorPropertiesofBonding&AntibondingStates(Firsthrexam,1999)■Hyperconjugationand"Negative"HyperconjugationThethreephosphitesillustratedbelowexhibita750–foldspaninreactivitywitha■AnomericandRelatedEffectstestelect
4、rophile(eq1)(Gorenstein,JACS1984,106,7831).■ReadingAssignmentforweek:+(RO)3P+El(+)(RO)3P–El(1)Kirby,StereoelectronicEffectsOMeOCarey&Sundberg:PartA;Chapter1PPOOMeFleming,Chapter1&2OPOOOOFukui,Acc.Chem.Res.1971,4,57.(pdf)ABCCurnow,J.Chem.Ed.1998,75,910(pdf)Rankthephosphitesfromtheleastto
5、themostnucleophilicandAlabugin&Zeidan,JACS2002,124,3175(pdf)provideaconciseexplanationforyourpredictedreactivityorder.Monday,D.A.EvansSeptember15,20031-01-CoverPage9/15/038:56AMD.A.EvansAnIntroductiontoFrontierMolecularOrbitalTheory-1Chem206UniversalEffectsGoverningChemicalReactions■Ste
6、reoelectronicEffectsTherearethree:Geometricalconstraintsplacedupongroundandtransitionstates■StericEffectsbyorbitaloverlapconsiderations.Nonbondinginteractions(VanderWaalsrepulsion)betweensubstituentswithinamoleculeorbetweenreactingmoleculesFukuiPostulateforreactions:MeMe"Duringthecourse
7、ofchemicalreactions,theinteractionofSN2–Nu:CBrNuCRBr:thehighestfilled(HOMO)andlowestunfilled(antibonding)RRRmolecularorbital(LUMO)inreactingspeciesisveryimportanttothestabilizationofthetransitionstructure."ROROHOOmajorHH■GeneralReactionTypesMeMe2CuLiROMeRadicalReactions(~10%):A
