碩士 / 國立中央大學 / 化學研究所 / 94 / 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.
| Identifer | oai:union.ndltd.org:TW/094NCU05065049 |
| Date | January 2006 |
| Creators | Yi-Wei Hsieh, 謝奕偉 |
| Contributors | Duen-Ren Hou, 侯敦仁 |
| Source Sets | National Digital Library of Theses and Dissertations in Taiwan |
| Language | zh-TW |
| Detected Language | English |
| Type | 學位論文 ; thesis |
| Format | 104 |
Page generated in 0.0129 seconds