6羰基双环310己烷衍生物的不对称norrishyang光反应研究 word格式.docxVIP

ClassifiedIndex:O64U.D.C:540.54DissertationfortheDegreeofMasterinScienceASYMMETRICNORRISH/YANGPHOTOREACTIONOF6-CARBONYLSUBSTITUTED BICYCLO[3.1.0]HEXANECandidate：BaofuQiuSupervisor：Prof.WujiongXiaAcademicDegreeAppliedfor:MasterofScienceSpeciality：PhysicalChemistryAffiliation：School ofScienceDateofDefence：June,2010Degree-Conferring-Institution:：HarbinInstituteofTechnology摘要利用固相光化学反应，进行分子的不对称合成是一种新的合成方法。它不仅发挥了光化学反应和固相反应本身的特点及优势，更重要的是在不对称合成领域提出了一个新思路，具有很广阔的应用与研究价值。本论文的研究内容有两个方面，以二环庚二烯为起始原料，经过过氧乙酸和硝酸银氧化，重氮甲烷酯化，氢化锂铝还原，叔丁基二甲基氯硅烷保护，硼氢化氧化，乙酰基保护，脱掉TBS保护，利用swern氧化法将醇氧化成醛，进行格氏反应等步骤合成中间体6-羰基双环[3.1.0]己烷衍生物。光照反应后，经过分子内的Norrish/Yang反应得到具有两个手性中心的环戊烯衍生物，这个目标产物可以用来合成前列腺素类药物；尝试改变实验条件及不同的实验方法，提高反应产率。环戊烯衍生物是合成前列腺素及衍生物等手性药物的重要中间体。本论文的研究，合成了多取代的环戊烯衍生物，对前列腺素类药物的合成具有着积极意义，同时也对将对利用光化学反应合成手性药物的研究提供一定的科学依据。关键词：固相光化学；不对称合成；环戊烯衍生物；Norrish/Yang 反应ⅠAbstractThenewasymmetricsynthesisusingsolid-phasephotochemicalreactionsisdevelopedbyprofessorScheffergroup.Thisapproachnotonlyappliescharactersandadvantages ofphotochemicalreactionandsolid phasereaction,butmore importantly,is anewideainthefieldofasymmetricsynthesisandhaveaverybroadapplicationandresearchvalue.Thisapproachhasraisedgreatinterestandconcernamongthechemists.Themainresearchcontentsofthis paperhastwoaspects,weuse[2.2.1] heptadieneasthestartingmaterial,afteroxidationofperaceticacidandsilvernitrate,diazomethaneesterification,lithiumaluminumhydridereduction,tert-butyldimethyl chlorosilaneprotectionborohydrideoxidation,acetylprotection,removeTBSprotection,oxidationofalcoholtoaldehydesusingswernoxidation,toformreactionstepsynthesisofintermediate6-carbonylsubstitutedbicyclo[3.1.0]hexanederivatives,Afterphotoreaction,cyclopentenederivativeswithtwochiralcentersisabtainedthroughintramolecularNorrish/Yangreaction,thetargetproductcanbeusedtosynthesizeprostaglandin-typedrugs;wetrytochangetheexperimentalconditionsanddifferentreagentsandincreasetheyield.Cyclopentenederivativesareveryimportantintermediatestosynthesizeprostaglandinsanditsderivatives.Therefor