Sequencing of three-component olefin metatheses: total synthesis of either (+)-gigantecin or (+)-14-deoxy-9-oxygigantecin.
[Structure: see text] An efficient, flexible, and highly convergent strategy for accessing skipped bis-THF containing Annonaceous acetogenins is demonstrated by the synthesis of each of (+)-gigantecin (1) and its constitutional isomer (+)-14-deoxy-9-oxygigantecin (11). The skeleton of each compound is produced, at will, from the same precursors via a three-component ring-closing/cross-metathesis sequence that differs only in the ordering of the RCM vs CM events. Another notable aspect is the use of in situ epoxide-closing and -opening of iodohydrins with dimethylsulfonium methylide to provide inverted allylic alcohols.
Hoye
Thomas R
TR
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA. hoye@chem.umn.edu
Eklov
Brian M
BM
Jeon
Junha
J
Khoroosi
Mila
M
D000475:Alkenes / Q000737:chemistry; D029061:Annonaceae / Q000737:chemistry; D000972:Antineoplastic Agents, Phytogenic / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D005663:Furans / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D007769:Lactams; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D015394:Molecular Structure; D013237:Stereoisomerism
C519416:14-deoxy-9-oxygigantecin; D000475:Alkenes; D000972:Antineoplastic Agents, Phytogenic; D005663:Furans; D007769:Lactams; D007783:Lactones; C064403:gigantecin