| DC 欄位 |
值 |
語言 |
| DC.contributor | 化學學系 | zh_TW |
| DC.creator | 謝奕偉 | zh_TW |
| DC.creator | Yi-Wei Hsieh | en_US |
| dc.date.accessioned | 2006-7-24T07:39:07Z | |
| dc.date.available | 2006-7-24T07:39:07Z | |
| dc.date.issued | 2006 | |
| dc.identifier.uri | http://ir.lib.ncu.edu.tw:444/thesis/view_etd.asp?URN=93223022 | |
| dc.contributor.department | 化學學系 | zh_TW |
| DC.description | 國立中央大學 | zh_TW |
| DC.description | National Central University | en_US |
| dc.description.abstract | 本論文為Pumiliotoxin、Allopumiliotoxin中間物1、2及河馬海棉酸A主結構53之合成研究。
化合物1為合成Pumiliotoxin的關鍵中間物。以L-脯胺酸作為起始物，經由保護胺基、酯化、甲基化後得到甲基酮化合物15。三氟醋酸對甲基酮15去保護後用乙烯葛林納試劑藉由螯合控制得到了d.e. > 95 % 之三級醇36。化合物36醯胺化後得到37，化合物37經由閉環置換及氫化得到了Pumiliotoxin中間物1。
化合物2為合成Allopumiliotoxin的中間物。以1為起始物，預期經由保護、環氧化、還原、氧化、去保護後得到化合物2。
化合物53為河馬海棉酸A的主架構。本論文描述了經由醇59和末端二取代烯55以氧化銀(silver oxide)條件進行耦合得到雙烯化合物64。進行閉環置換後得到具有環內雙鍵之哌喃65。化合物65以鈀金屬催化甲酸還原反應得到具有環外末端雙鍵之哌喃66。未來將會對66進行α亞甲基化得到68，最後鹼性條件下水解得到河馬海棉酸A的主要結構53。 | zh_TW |
| dc.description.abstract | This thesis describes the syntheses of the three key intermediates 1, 2 and 53 to Pumiliotoxin, Allopumiliotoxin and Hippospongic acid A .
L-proline was converted to the N-BOC protected pyrrolidine ketone 15 through protection, esterification and methylation. Treating compound 15 with trifluoroacetic acid,and then vinylmagnesium bromide provided alcohol 36 with high diastereoselectivity by “chelation control”. After ring-closing metathesis and hydrogenation, Pumiliotoxin key intermediate 1 was obtained.
After protection, expoxidation, reduction, oxidation and deprotection, indolizidine 1 should be converted to Allopumiliotoxin key intermediate 2.
Compound 53 is the main framework of Hippospongic acid A . Coupling of alcohol 59 and ester 55 with silver oxide provided diene 64. After ring-closing metathesis and palladium-catalyzed formate reduction, compound 64 was converted to pyran 66 with a terminal alkene substituent. In the future, we expect that we can get α-methylene substituted ester 68 by α-methylenation. Compound 53 can be obtained after hydrolysis. | en_US |
| DC.subject | 河馬海棉酸 | zh_TW |
| DC.subject | Hippospongic acid A | en_US |
| DC.subject | Allopumiliotoxin | en_US |
| DC.subject | Pumiliotoxin | en_US |
| DC.title | Pumiliotoxin、Allopumiliotoxin中間物及
河馬海棉酸A(Hippospongic acid A)主結構之合成研究 | zh_TW |
| dc.language.iso | zh-TW | zh-TW |
| DC.type | 博碩士論文 | zh_TW |
| DC.type | thesis | en_US |
| DC.publisher | National Central University | en_US |