Highly diastereoselective formation of spirocyclic compounds via 1,5-hydrogen transfer: a total synthesis of (-)-erythrodiene.
[reaction: see text] A highly stereoselective synthesis of (-)-erythrodiene starting from 4-isopropylcyclohexanone is described. The key reactions are an asymmetric methoxycarbonylation of the starting ketone and a highly diastereoselective radical cascade involving addition of a phenylthiyl radical to a terminal alkyne followed by a 1,5-hydrogen transfer and a 5-exo-cyclization.
Lachia
Mathilde
M
Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012 Bern, Switzerland.
Dénès
Fabrice
F
Beaufils
Florent
F
Renaud
Philippe
P
D002722:Chlorobenzenes / Q000737:chemistry; D003500:Cyclization; D003510:Cyclohexanes / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D015394:Molecular Structure; D010636:Phenols / Q000737:chemistry; D012997:Solvents; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry; D013696:Temperature
D002722:Chlorobenzenes; D003510:Cyclohexanes; D007659:Ketones; D010636:Phenols; D012997:Solvents; D013141:Spiro Compounds; D013438:Sulfhydryl Compounds; C511223:erythrodiene; C042983:thiophenol; D006859:Hydrogen; C031294:chlorobenzene