手性配體TATOL的合成及其在氨基酸手性合成中的應(yīng)用.pdf

1、南開大學(xué)碩士學(xué)位論文手性配體TATOL的合成及其在氨基酸手性合成中的應(yīng)用姓名：韓軍申請(qǐng)學(xué)位級(jí)別：碩士專業(yè)：有機(jī)化學(xué)指導(dǎo)教師：王積濤2001.5.1AbstractThedevelopmentofversatileandnewmethodologiesforthesynthesisofnaturalandnonnaturalcLaminoacidsinopticallypureformisanimportantandchallenging

2、syntheticendeavourfororganicchemistsnowadaysduetotheircentralroleinchemistryandbiologyUptonowscientistshavealreadydevelopedalargenumberofmaturemethodsinproducinghigheevaluechiralaaminoacids，thefollowingareamongthemostwid

3、elyused：stereoselectivelyelectrophilicadditionofglycineequivalentdirectedbychiralauxiliaryorintromolecularchiralcenterelectrophilicadditionofglycineequivalentinthepresenceofchiralphasetransfercatalyst，specialconstruction

4、ofaminoacid—containedmolecularthatenabletheelectrophileapproachcentralCpreferablyincertaindirection，etcInthisthesis，agroupofnovelchiraldiolswithbulkysubstituents～TATOLsweredesignedandproducedbyusingstructurecombinationme

5、thods，varioussubstituentswereintroducedintotheleadcompound，whichformedachiralligandlibraryStartingfromtartaricacid，thesecompoundswereobtainedthroughthefollowingprocedure：acetalformation，Grignardreaction，elaborationofoc，儀

6、’dihydroxygroupsandremovalofacetalprotectionSomerepresentativecompoundsinthislibrarywereappliedinthechiralsynthesisof值一aminoacidsbyusingstandardprocedureThetetraphenylsubstitutedchiraldiolwasfoundtobeanexcellentchiralaux

7、iliaryinthemethylationofNsalicylidenephenylaIaninatesubstrateTheexperimentalresultsclearlydemonstratethattheeevaluesofaminoacidsaregreatlyaffectedbythebulkinessofTATOLsidechainsWiththeaimtoimprovetheefficiencyofTATOLinst

8、ereoselectivereaction，WeenlargethebulkinessofitssidechainsOurapproachisbasedonthefollowingconcept：substituteLPPDDOL14一hydroxygroupswithCI，thenintroducenucleophilestotheintermediate，afterhydrogonationwithPd／Cascatalysisan