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1、ComputationalstudiesanddesignofbiomolecularDiels-AldercatalysisMATSLINDERDoctoralThesisStockholm,Sweden2012TRITACHEReport2012:34KTHSchoolofChemicalScienceandEngineeringISSN1654-1081SE-10044StockholmISBN978-91-7501-435-7SWEDENAkademiskavhandlingsommedtil
2、lståndavKunglTekniskahögskolanframläggestilloffentliggranskningföravläggandeavteknologiedoktorsexamenikemimedinriktningmotfysikaliskkemifredagenden21september2012klockan10.00iSalK1,KunglTekniskahögskolan,Teknikringen56,Stockholm.Avhandlingenförsvaraspåen
3、gelska.FakultetsopponentProfessorKendallN.HoukUniversityofCalifornia,LosAngeles©MatsLinder,September2012Tryck:E-printAB,Oxtorgsgatan9–11,11157StockholmiiiTomyfamily."Sciencemaysetlimitstoknowledge,butshouldnotsetlimitstoimag-ination."—BertrandRusselivAb
4、stractMatsLinder2012DoctoralThesis:"ComputationalstudiesanddesignofbiomolecularDiels-Aldercatalysis"AppliedPhysicalChemistry,ChemicalScienceandEngineering,KTHRoyalInstituteofTechnology,S-10044Stockholm,Sweden.TheDiels-Alderreactionisoneofthemostpowerful
5、synthetictoolsinorganicchemistry,andasymmetricDiels-Aldercatalysisallowsforrapidcon-structionofchiralcarbonscaffolds.Forthisreason,considerableefforthasbeeninvestedindevelopingefficientandstereoselectiveorgano-andbiocata-lysts.However,Diels-Alderisavirtuall
6、yunknownreactioninNature,andtoengineeranenzymeintoaDiels-Alderaseisthereforeachallengingtask.De-spiteseveralsuccessfuldesignsofcatalyticantibodiessincethe1980’s,theircatalyticactivitieshaveremainedlow,andnotrueartificial’Diels-Alderase’enzymewasreportedb
7、efore2010.Inthisthesis,weemploystate-of-the-artcomputationaltoolstostudythemechanismoforganocatalyzedDiels-Alderindetail,andtoredesignexistingenzymesintointermolecularDiels-Aldercatalysts.PapersI–IVexplorethemechanisticvariationswhenemployingincreasingl
8、yactivatedreactantsandtheeffectofcatalysis.Inparticular,therelationbetweenthetraditionallypresumedconcertedmechanismandastepwisepathway,formingonebondatatime,isprobed.PapersV–Xdealwithenzymedesignandthecompu-tationalaspectsofpredi
