吳學亮Wu, Hsyueh-Liang蕭萱霈Hsiao, Hsuan-Pei2022-06-082026-08-242022-06-082021https://etds.lib.ntnu.edu.tw/thesis/detail/e53379a477209678f8b067176a7779b9/http://rportal.lib.ntnu.edu.tw/handle/20.500.12235/117234本篇論文論述利用一價銠金屬與掌性雙環[2.2.2]雙烯配基L1c、L1f形成錯合物後，催化環狀α-重氮-β,γ-不飽和酯類化合物11或是鏈狀α-重氮-β,γ-不飽和酯類化合物8，形成銠金屬碳烯(rhodium carbenoid)中間體，再使含氮親核試劑9進行具有位向選擇性的不對稱加成反應。反應成功地合成出一系列具有掌性中心之環狀γ-胺基α,β-不飽和酯類化合物12，產率為16–55%，鏡像超越值為26–91%；及鏈狀γ-胺基α,β-不飽和酯類化合物10，產率為9–60%，鏡像超越值為84–>99.5%。將具有掌性中心的γ胺基α,β-不飽和乙酯化合物10hb經由數步反應後，可合成出β位具有取代基的γ胺基酸-普瑞巴林衍生物101。This thesis describes the regioselective and enantioselective of rhodium(I)-catalyzed asymmetric N-H insertion reaction of α-diazo β,γ-unsaturated esters 11, 8 with anilines 9. In presence of 3.0 mol % Rh (I)-catalyst in situ generated from [RhCl(C2H4)2]2 and chiral bicyclo [2.2.2] octadiene ligand L1c, L1f . The reaction was afforded enantiorich regid γ-amino α,β-unsaturated esters 12 in 16–55% yield with 26–91% ees and linear γ-amino α,β-unsaturated esters 10 in 9–60% yield with 84–>99.5% ees. Synthesis of pregabalin derivative 101 was performed to prove feasibility of this method.一價銠金屬銠金屬碳烯中間體重氮酯類掌性雙環[2.2.2]雙烯配基rhodium(I)-catalyzedrhodiumcarbenoidα-diazoesterchiral bicyclo [2.2.2] octadiene ligand學術論文