多取代環己烷化合物之有機催化連鎖環化反應
| dc.contributor | 陳焜銘 | zh_TW |
| dc.contributor.author | 簡崇瀚 | zh_TW |
| dc.date.accessioned | 2019-09-04T09:19:57Z | |
| dc.date.available | 2018-7-24 | |
| dc.date.available | 2019-09-04T09:19:57Z | |
| dc.date.issued | 2013 | |
| dc.description.abstract | 藉由二分子一鍋化反應，進行不對稱有機催化連鎖反應，發展鏡像選擇性全取代二螺環己烷。本實驗使用2-芳香環亞甲基氫茚-1‚3-二酮和醛類，加入5 mol%的‚-L-雙苯環脯胺醇矽醚有機催化劑及 20 mol%的1‚4-二氮雜二環[2.2.2]辛烷，在二甲基二醯胺為溶劑及-20 oC下，進行Michael/Michael/aldol連鎖反應，得到全取代二螺環己烷，其有不錯的產率及非常好的立體選擇性(>95:5 dr 和 高達 99% ee)；除此之外，經由單晶繞射X-ray確認其產物絕對立體組態；另一方面，本實驗也嘗試使用2-(4-硝基苯亞甲基)-氫茚-1‚3-二酮及丙烯醛，以20 mol%的掌性三級胺進行催化，在二甲基二醯胺為溶劑及0 oC下，經由Michael/Michael/cyclization連鎖反應，可得到五取代二螺環己烷，其產率及鏡像選擇性在持續探討中。本實驗成功利用二種不同策略，進行合成多取代環己烷，並且建構兩個四級碳中心，在未來合成發展上極具經濟效益。 | zh_TW |
| dc.description.abstract | An interesting asymmetric organocatalytic domino reaction by using two components have been developed that gives fully substituted dispirocyclohexanes in one pot. In this study‚ treatment of 2-arylideneindane-1‚3-diones with aldehydes using a catalytic amount of ‚-L-diphenylprolinol silyl ether (5 mol%) and DABCO (20 mol%) in DMF at -20 oC to give fully substituted dispirocyclohexanes via domino Michael/Michael/aldol process with moderate chemical yields and high-to-excellent stereoselectivities (>95:5 dr and up to 99% ee). Besides‚ the absolute stereochemistry is determined by single crystal X-ray analysis of product. On the other hand‚ in another study‚ reaction was carried out under 0 oC by using the (2-(4-nitro-benzylidene)-indan-1‚3-dione) and acrolein as starting materials in DMF in the presense of chiral tertiary amine catalyst (20 mol%) to give pentasubstituted dispirocyclohexanes via cascade Michael/Michael/cyclization process but the chemical yields and enantioselectivity has not been optimized. Successfully synthesis of multisubstituted cyclohexanes and construct two all-carbon quaternary by using two diferrent strategy are more commercial for another synthetic development in the future. | en_US |
| dc.description.sponsorship | 化學系 | zh_TW |
| dc.identifier | GN060042033S | |
| dc.identifier.uri | http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN060042033S%22.&%22.id.& | |
| dc.identifier.uri | http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/100350 | |
| dc.language | 中文 | |
| dc.subject | 一鍋化 | zh_TW |
| dc.subject | 不對稱有機催化連鎖反應 | zh_TW |
| dc.subject | 多取代二螺環己烷 | zh_TW |
| dc.subject | domino/cascade | en_US |
| dc.subject | dispirocyclohexanes | en_US |
| dc.subject | Michael/Michael/cyclization | en_US |
| dc.title | 多取代環己烷化合物之有機催化連鎖環化反應 | zh_TW |
| dc.title | Organocatalytic Synthesis of Functionalized Cyclohexanes via Domino Michael/Michael/Cyclization Reaction | en_US |
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