多配位點(diǎn)氨基酸衍生物催化的不對(duì)稱Reformatsky反應(yīng)以及雙手性中心西佛堿銅絡(luò)合物催化的不對(duì)稱環(huán)丙烷化反應(yīng).pdf

1、中國(guó)科學(xué)技術(shù)大學(xué)博士學(xué)位論文多配位點(diǎn)氨基酸衍生物催化的不對(duì)稱Refmatsky反應(yīng)以及雙手性中心西佛堿銅絡(luò)合物催化的不對(duì)稱環(huán)丙烷化反應(yīng)姓名：蔣昌盛申請(qǐng)學(xué)位級(jí)別：博士專業(yè)：有機(jī)化學(xué)指導(dǎo)教師：尤田耙2002.4.1AbstractTherearealltwopartsinthethesisOneofthemiSabouttheasymmetricReformatskyreactioncatalyzedbyaminoacidderivativ

2、eswithmulti—coordinationgroups；Anotheroneisasymmetriccyclopropanationcatalyzedbycopper一(Schiffbase)complexeswithdoublechiralcentersThecatalyticasymmetricReformatskyreactionisveryimportantintheareaofsynthesizingchiralBhyd

3、roxylester(acid)someofwhichhavebiologicactivityButtherehasbeennoveryeffectivechiralcatalystforthisreactionbynowAseriesofaminoacidmethylesters，lineardipeptides，cyclodipeptidesandaminoacidderivativesofSchiffbasewithmulti—c

4、oordinationgroups，someofwhichhaverigidstructureorC2symmetryweredesignedandsynthesizedinthispaperThenaturalaminoacidswithcoordinationgroupontheirsidechainsuchasserine，threonine，tyrosine，tryptophanwereusedasstartingmateria

5、lAllthesechiralligandswereusedtocatalyzetheasymmetricReformatskyreactionTheinfluencesofstructureandamountofcatalyst，reactiontemperature，solventandstructureofsubstratetotheenantioselectiVitywereinvestigatedTheproduct’Sbes

6、teevalueisupto64％Amongallthechiralligandsweused，theaminoacidderivativeofSchiffbaseandcyclodipeptidesarebetterthantwoothersandthederivativeofLPheTryOMeisbestamongtheaminoacidderivativeofSchiffbaseandtheC【L—SerL—Ser]whichh

7、asC2symmetryisbestamongthecyclo—dipeptidePossiblecatalyticmechanismsofsomechiralligandswereproposedbasedontheseresultsThecopper(Schiffbase)complexisonecategoryoftheimportantcatalystsfortheasymmetriccyclopropanationreacti

8、onUptonowallthecopper(Schiffbase)complexesthathavebeenappliedtocatalyzethisreactionhaveonlyonechiralcenterthecarbonattachedtOthenitrogenatomandthecatalyticmechanismisstillnotveryclearAseriesofacopper(Schiffbase)complexwi

9、thdoublechiralcentersweresynthesizedfromfourstereoisomersof1，2diphenyl一2amino—ethanolandappliedtocatalyzetheasymmetriccyclopropanationofolefinswithdiazoestersinthispaperTheinfluencesofstructureandamountofcatalyst，reactio

10、ntemperature，solventandstructureofsubstratetotheenantioselectiVitywereinvestigatedTheproduct’Sbesteevalueisupto986％Theseresultsindicatedthattheconfigurationofthecarbonatomattachedtothenitrogenatomofthecomplexdominatesthe