Sulfonyl-stabilized oxiranyllithium-based approach to polycyclic ethers. Convergent synthesis of the ABCDEF-ring system of yessotoxin and adriatoxin.
Convergent synthesis of the ABCDEF-ring system of yessotoxin and adriatoxin, marine polycyclic ether toxins causative of diarrheic shellfish poisoning, has been accomplished. The A-ring fragment was constructed by coupling of an appropriately functionalized sulfonyl-stabilized oxiranyl anion and a triflate prepared from an erythritol derivative. An iterative protocol of the oxiranyl anion strategy was also applied for the construction of the DEF-ring fragment. The triflate derivatives of the A-ring and the DEF-ring fragments were connected with lithium acetylide. The resulting acetylene derivative was further transformed into the hexacyclic ABCDEF fragment via oxidation of the acetylene unit to 1,2-diketone, double methyl acetal formation, and reductive etherification.
Mori
Yuji
Y
Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503, Japan. mori@ccmfs.meijo-u.ac.jp
Nogami
Kouichi
K
Hayashi
Hiasafumi
H
Noyori
Ryoji
R
D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D004988:Ethers, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D008094:Lithium / Q000737:chemistry*; D015394:Molecular Structure; D008978:Mollusk Venoms; D035964:Oxocins / Q000138:chemical synthesis* / Q000737:chemistry; D013057:Spectrum Analysis
D004987:Ethers; D004988:Ethers, Cyclic; D008978:Mollusk Venoms; D035964:Oxocins; C482966:adriatoxin; D008094:Lithium; C066632:yessotoxin