Enantioselective syntheses of pachastrissamine and jaspine A via hydroxylactonization of a chiral epoxy ester.
A new enantioselective total synthesis of pachastrissamine (jaspine B) was achieved from a known alpha,beta-unsaturated aldehyde by utilizing Córdova's asymmetric epoxidation as the chirality-inducing step. The 2,3-cis stereochemistry of pachastrissamine was established via intramolecular epoxide ring opening of a gamma,delta-epoxy-alpha,beta-unsaturated ester intermediate coupled with oxy-Michael cyclization. Treatment of pachastrissamine with tetrahydro-2-furanol under acidic conditions led to smooth oxazolidine ring formation, furnishing jaspine A in a high yield.
Urano
Hiroyuki
H
Laboratory of Applied Bioorganic Chemistry, Graduate School of Agricultural Science, Tohoku University, Sendai, Japan.
Enomoto
Masaru
M
Kuwahara
Shigefumi
S
D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D003500:Cyclization; D004852:Epoxy Compounds / Q000737:chemistry*; D004952:Esters / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry*; D013110:Sphingosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity
D019086:Bridged Bicyclo Compounds, Heterocyclic; D004852:Epoxy Compounds; D004952:Esters; D007783:Lactones; C548354:jaspine A; C468594:pachastrissamine; D013110:Sphingosine