本篇論文研究分為兩個部分： (1) 利用掌性的雙烯雙醇52為起始物合成(-)-Lentiginosine。保護後 之62先與丙烯醛80進行第一次的交叉置換反應，並將另一個羥 基也作上保護。然後進行乙烯基加成和氧化反應來合成二烯酮 66，再利用苯甲胺48a經由非鏡像選擇性之double aza-Michael 加成反應進行合環形成中間產物哌啶酮82。未來希望藉由氫化/ 合環反應得到吲哚啶88，並將吲哚啶88作去保護合成出天然物(-)-Lentiginosine (1)。 (2) 利用芳香性氨基甲酸酯衍生物與氫化鋁鋰進行還原反應得到半 縮胺，並討論酯基和胺基甲酸酯相對的反應性。 There are two topic in this thesis: (1) (-)-Lentiginosine (1) was synthesized using diene 52 as the strating material. The first cross metatheses (CM) reaction of protected 52 with acrolein 80 and the following protection, addition with vinylmagnesium bromide, and oxidation provided the dienone 66. The diastereoselective double aza-Michael addition of dienone 66 and benzylamine gave the piperidine compound 82. We expect that indolizidine 88 can be prepared by hydrogenation / cyclization. (-)-Lentiginosine (1) should be synthesized after deprotection. (2) The reduction reaction of derivatives of the aromatic carbamate and lithium aluminium hydride provided the hemiaminal. The relative reactivities of esters and carbamates were discussed.
