幾種手性配體的合成及其在手性亞砜不對(duì)稱合成中的應(yīng)用.pdf

1、湖南大學(xué)碩士學(xué)位論文幾種手性配體的合成及其在手性亞砜不對(duì)稱合成中的應(yīng)用姓名：羅成禮申請(qǐng)學(xué)位級(jí)別：碩士專業(yè)：藥物化學(xué)指導(dǎo)教師：匡永清20080424幾種手性配體的合成和其在手性亞砜不對(duì)稱合成中的應(yīng)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