幾種手性配體的合成及其在手性亞砜不對稱合成中的應用.pdf

1、湖南大學碩士學位論文幾種手性配體的合成及其在手性亞砜不對稱合成中的應用姓名：羅成禮申請學位級別：碩士專業(yè)：藥物化學指導教師：匡永清20080424幾種手性配體的合成和其在手性亞砜不對稱合成中的應用AbstractChiralsulfbxidesplayasignificantroleaschiralauxiliariesintheasymmetricorganicsynthesisAtthesametime，manybioactivem

2、oIeculeshavethestmcturalcharacteristicsofsulfloxide，andthefeatureandstrengthoftheirbioactivityarecloselycorrelatiVewiththeirstereoconfigurationThemostefncientwaytopreparechiralsulfbxidesistheasymmetricoxidationofprochira

3、lsulfidescatalyzedbychiralmetalcomplexesAmongthereportedchiralligands，somerequirecomplicatedsyntheticprocessesorcostiVestartingmaterials，somejustfitforanarrowspectrumofsubstratesWepreparedseveralchiralligandsfromnaturalc

4、hiralresourcesaccordingtoreportedprocedures，andfirstlyappliedthemintheasymmetricoxidationofprochiralsul6desTWochiralligandsl，2：5，6di—o—isopropylidene—D—mannitoIandl，2：5，6dio—cyclohexylidene—D—mannti01wereconVenientlyprep

5、aredbyketalizationofDmannitolwithacetoneorcyclohexanoneInthepresenceofchiraltitaniumcatalystfomedinsitufromTi(oiPr)4andthediolligand，sulfideswereoxidizedtosulfoxidebyTBHPinmoderateyields(29％～53％)andmoderateenantioselecti

6、vities(20％PP～54％Pe)Thebestresultswereobtainedunderthefollowingreactionconditions：sulfide／diol／Ti(Oi—Pr)4／H20=I／OI／005／l(molratio)；TBHP(70％inwater)asoxidant(2equiV)；CCl耷assolVent；O℃ThiscatalyticprotocolhasshowedtobefairIy

7、generalfDralkylarylsulfidesincludingthesulfideswithtwobulkygroupsN，N’一dibenzyl—D—tartaricaciddiamideandN，N’dicyclohexyl—DtartaricaciddiamideweresynthesizedbyammonolysisofDdiethyltartratewithbenzylamineandcyclohexylamineT

8、heircomplexeswithTi(Oi—Pr)4werefirstlyemployedinthecatalyticasymmetricoxidationofsulndewithTBHPastheoxidantat0℃Thecorrespondingsulfoxidewasobtainedin12％～32％ykldand6％PP—15％PPNosignincantimproVementoneitheropticalorchemica

9、lyieldswereachievedbychangingthereactionconditions4，6bis(9D—cinchonine)2，5diphenylpyrimidineandl，4一bis(9D—quinidine)phthalazinewefeeasilyobtainedfromthenaturalcinchonaalkaloidcinchonineandquinidineTheasymmetricsulfoxidat