吳學亮Wu, Hsyueh-Liang林冠宇Lin, Kuan-Yu2020-10-192025-12-312020-10-192020http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22G060742016S%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/111132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L3d形成錯合物，催化α-重氮-β,γ-不飽和酯類化合物11，反應形成銠金屬碳烯(rhodium carbenoid)中間體，與苯胺化合物12進行不對稱加成反應，成功地合成出一系列具有掌性中心之主要產物γ-胺基α,β-不飽和酯類化合物13，產率為6–85%，鏡像超越值為22–>99.5%，及副產物為具有掌性中心之α胺基β,γ-不飽和酯類化合物14，產率為15–54%，鏡像超越值為15–90%。將具有掌性的γ胺基α,β-不飽和乙酯化合物13al經由數步反應步驟，可合成出八氫吲哚衍生物99。An unprecedented rhodium (I)-catalyzed asymmetric N−H insertion reaction of α-diazo β,γ-unsaturated esters with available anilines 12 was reported. The asymmetric reaction permitted an efficient synthesis of chiral γ-amino α,β-unsaturated esters 13, in the presence of a Rh-catalyst in situ generated from [RhCl(C2H4)2]2 and chiral bicyclo [2.2.2] octadiene ligand L3d, with excellent enantioselectivities (22–>99.5% ees) and in good yields (6–85%) under mild conditions, along with α-amino β, γ-unsaturated esters 14in 15–54% yields and with 15–90% ees. The method was applied in the synthesis of a bioactive octahydroindole derivative 99 .一價銠金屬銠金屬碳烯重氮酯類掌性雙環[2.2.2]雙烯配基rhodium (I)-catalyzedrhodium carbenoidchiral bicyclo [2.2.2] octadiene ligandα-diazo β,γ-unsaturated esters