A bidirectional approach to the synthesis of a complete library of adjacent-bis-THF annonaceous acetogenins.
Thirty-six stereoisomers of bifunctional adjacent bis-THF (tetrahydrofuran) lactones have been synthesized, which can afford a complete library of the adjacent bis-THF Annonaceous acetogenins. The bis-THF lactones were synthesized, starting from the enantioselectively pure 8,9:12,13-(E,E and Z,E)-16-benzyloxy-5-hydroxy-hexadeca-1,4-olide, in a highly distereoselective manner using oxidative reactions, including rhenium(VII) oxides-mediated oxidative cyclization, Shi's asymmetric epoxidation, and Sharpless asymmetric dihydroxylation reactions. Using the nonsymmetrical bis-THF lactones, syntheses of two nonnatural acetogenins were achieved.
Das
Sanjib
S
The Skaggs Institute for Chemical Biology and the Department of Molecular Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
Li
Lian-Sheng
LS
Abraham
Sunny
S
Chen
Zhiyong
Z
Sinha
Subhash C
SC
D054378:Acetogenins; D029061:Annonaceae / Q000737:chemistry*; D000972:Antineoplastic Agents, Phytogenic / Q000138:chemical synthesis* / Q000494:pharmacology; D002412:Cations; D003500:Cyclization; D005233:Fatty Alcohols / Q000138:chemical synthesis* / Q000494:pharmacology; D005663:Furans / Q000138:chemical synthesis* / Q000494:pharmacology; D007783:Lactones / Q000138:chemical synthesis* / Q000494:pharmacology; D010084:Oxidation-Reduction; D012211:Rhenium / Q000737:chemistry; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
D054378:Acetogenins; D000972:Antineoplastic Agents, Phytogenic; D002412:Cations; D005233:Fatty Alcohols; D005663:Furans; D007783:Lactones; D012211:Rhenium