1.Room-Temperature B(OAc)3-Promoted Diels–Alder Reaction of Juglone with Styrenes: Total Syntheses of Tetrangulol and Anhydrolandomycinone. 2.Total Synthesis of Parimycin. 3. Synthetic Studies Toward Schisansphenin B.

• Main Authors: HUANG, JIUN-YI, 黃俊益
• Other Authors: Hsu, Day-Shin
• Format: Others
• Language: zh-TW
• Published: 2017
• Online Access: http://ndltd.ncl.edu.tw/handle/nsnwt8

博士 === 國立中正大學 === 化學暨生物化學研究所 === 105 === Abstract: This thesis describes the total syntheses of tetrangulol, anhydrolandomycinone, parimycin and schisansphenin B. In the first topic, we developed a simple method to synthesize angucyclinones; The Diels–Alder reaction of juglone with various styrenes in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was promoted by B(OAc)3 at room temperature. The reaction proceeded smoothly and gave the products in 32%~82% yield and with excellent regioselectivity. We successfully applied this methodology to the total syntheses of tetrangulol and anhydrolandomycinone from Omethylnaphthazarin (56) and bromostyrene 7m in 4 synthetic steps with 53% overall yield and 4 synthetic steps with 42% overall yield, respectively. In the second topic, the first total synthesis of parimycin was accomplished from O-methylnaphthazarin (56) in 10 synthetic steps. The key steps in this synthesis were B(OAc)3-promoted intermolecular Diels- Alder reaction of (56) and diene 108, DMSO-iodine-promoted oxidative cyclization, and sodium dithionite reduction. In the third topic, the synthetic study of schisansphenin B was commenced with 1,3-cyclopentadione in 7 steps. The key steps in this synthesis were redox-relay Heck coupling reaction of alkene and triflate, intramolecular Stetter reaction and Tiffeneau-Demjanov-type ring expansion to construct the spiro[4.5]decane skeleton. Key words: Diels-Alder reaction、B(OAc)3、Juglone、Styrene、Heck coupling reaction、Intramolecular Stetter reaction、Spiro.