1.Total Syntheses of Cladoacetal A and Cladoacetal B, and the Confirmation of their Absolute Configurations 2.Total Syntheses and Stereochemistry Revisions of Phellinusfuran A and Phellinusfuran B 3.Synthetic Studies toward Allosecurinine

• Main Authors: LIN, SHIH-CHUNG, 林世忠
• Other Authors: HSU, DAY-SHIN
• Format: Others
• Language: zh-TW
• Published: 2017
• Online Access: http://ndltd.ncl.edu.tw/handle/j59drt

博士 === 國立中正大學 === 化學暨生物化學研究所 === 105 === This thesis describes the total syntheses of cladoacetal A, cladoacetal B, phellinusfuran A, phellinusfuran B and allosecurinine. In the first topic, the first enantioselective syntheses of cladoacetals A (1a, overall yield: 16%) and B (1b, overall yield: 34%) from crotonaldehyde in nine and seven steps, respectively, have been accomplished. Sharpless asymmetric dihydroxylation, Suzuki coupling, and acid-catalyzed intramolecular acetalization were the key steps in the syntheses. The absolute configuration of natural (+)-cladoacetal A was affirmed to be 1S,3S,4R, where as that of (−)-cladoacetal B was affirmed to be 1R,3S,4S. In the second topic, we described the symthetic studies toward phellinusfuran A (23) and B (24), two novel furan derivatives, were isolated from Phellinus linteus in 2006, which showed anti-complement activity. The known aldehyde 29 was used as the starting material in this synthesis. Lithium aluminum hydride reduction, Morita-Baylis-Hillman reaction, and acid-catalyzed intramolecular cyclization were the key steps. In the third topic, we described synthetic studies toward the racemic allosecurinine. The key steps in this process were 1,3-dipolar cycloaddition, Davis -hydroxylation and Weinreb amide addition. We also confirmed the relation configuration of important intermediate 77 by NOESY and X-ray single crystal analysis.