吳學亮Wu, Hsyueh-Liang呂怡柔Lu, Yi-Rou2020-10-192025-09-102020-10-192020http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22G060742051S%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/111155本篇論文探討利用一價銠金屬及掌性雙環[2.2.1]雙烯配基L1形成之催化劑催化芳香基硼酸試劑48對環狀α,β-不飽和β-酮酯47進行不對稱1,4-加成反應。生成加成產物46為單一非鏡像異構物有產率67–99%及鏡像超越值66–99%。此加成產物46可再進行烷基化反應(C-alkylation),建構掌性四級碳之產物45,其產物45產率43–94%及鏡像超越值66–98%。本論文探討利用此方法應用在合成天然物(−)-Cephalotaxine之可能性This thesis studies the asymmetric 1,4-addition reaction of arylboronic acids 48 to cyclic α,β-unsaturated β-ketoester 47 catalyzed by a Rh(I)/chiral diene ligand L1 catalyst. The adducts 46 were obtained as a single diastereomer in up to 99% yield and with up to 99% ee. Furthermore, the adducts 46 underwent C-alkylaion reaction to provide products 45 with a chiral quaternary stereogenic center in up to 94% yield and with up to 98% ee. This method was used for the synthetic study toward the total synthesis of natural product (−)-Cephalotaxine.一價銠金屬掌性雙環[2.2.1]雙烯配基環狀α,β-不飽和β-酮酯不對稱1,4-加成反應天然物Rh(I)/chiral diene ligand catalystasymmetric 1,4-addition reactionα,β-unsaturated β-ketoesternatural product利用一價銠金屬進行不對稱1,4-加成反應對三尖杉鹼天然物全合成之合成研究A Synthetic Study Toward the Total Synthesis of (−)-Cephalotaxine Using Rh(I)-Catalyzed Enantioselective 1,4-Addition Reaction