利用1炔基Fischer卡宾化合物的N杂环有机合成-有机化学专业论文.docxVIP

AbstractABSTRACT Abstract ABSTRACT Zhaoyan Zheng(Organic Chemistry) Supervised by Prof．Xiuwen Han and Prof．Zhengkun Yu Novel N-heteroeyclic structures v／a 1-alkynyl Fischer carbene complexes were constructed．Efficient dernetalation methods ofFischer carbene complexes to obtain nitrogen·containing heteroeyelic compounds had been developed． Reactions of substituted pyrazolinones with 1-alkynyl Fischer carbene complexes(OC)sM=C(OEt)C=-CPh(M=Cr,聊afforded a series of bieyclic N-heterocyclie Fischer carbene complexes．The effect of substituents of pyrazolinones was studied．Suitable oxidants such as pyridine-N-oxide(PNO)and m—chloroperoxybenzoic acid f聊-CPBA)were found to oxidatively demetalate the newly formed complexes，forming N-heterocyclic organic products including ! strongly fluorescent mixed bimanes． Demetalation of Fischer earbene complexes was systematically investigated using oxidizing and reducing agents．Oxidative demetalafion of 2-alkoxy Fischer mono-and biscarbene complexes Was efficiently carried out with pyridine-N-oxide ONO)．Fischer alkoxy biscarbene complexes realized stepwise oxidative demetalation under controlled condition,resulting in ester-monocarbene complexes and diester products，respectively．Sulfuration and selenylation of Fischer biscarbene complexes were achieved by means of加—Jfm generated SCO and SeCO，efficiently affording thio—and sclenocarboxylates．Demetalation of Fischer monocarbene complexes was also investigated with the same method． AbstraetN-Heterocyclic Abstraet N-Heterocyclic Fischer biscarbene complexes were synthesized from the reactions of O-a埘l laetims with 1-alkynyl Fischer carbene complexes． Chemoselective oxidatioa ofthe bisearbene complexes was stepwisely carried out with pyridine-N-oxide(PNO)to generate partially and completely demetalated products．Si02-promoted rearrangement of a chromium biscarbene complex and its thermal annelation were explored．The reaction mechanisms were discussed and the possible reaction pathways