TY - JOUR
T1 - Diastereoselective total synthesis of both enantiomers of epolactaene
AU - Hayashi, Yujiro
AU - Kanayama, Jun
AU - Yamaguchi, Junichiro
AU - Shoji, Mitsuru
PY - 2002/12/27
Y1 - 2002/12/27
N2 - A stereocontrolled total synthesis of both the (+)- and (-)-epolactaene ((+)- and (-)-1) enantiomers from tetrahydropyran-2-ol is described. The following reactions in this synthesis are particularly noteworthy: (1) the stereoselective construction of the conjugated (E,E,E)-triene by a combination of kinetic deprotonation and thermodynamic equilibration, (2) the E-selective Knoevenagel condensation of β-ketonitrile 33 with a chiral 2-alkoxyaldehyde, (3) a diastereoselective epoxidation achieved using a bulky nucleophile (TrOOLi) and an appropriate protecting group, (4) the mild hydrolysis of an α-epoxy nitrile by silica gel on TLC facilitated by hydroxyl-mediated, intramolecular assistance.
AB - A stereocontrolled total synthesis of both the (+)- and (-)-epolactaene ((+)- and (-)-1) enantiomers from tetrahydropyran-2-ol is described. The following reactions in this synthesis are particularly noteworthy: (1) the stereoselective construction of the conjugated (E,E,E)-triene by a combination of kinetic deprotonation and thermodynamic equilibration, (2) the E-selective Knoevenagel condensation of β-ketonitrile 33 with a chiral 2-alkoxyaldehyde, (3) a diastereoselective epoxidation achieved using a bulky nucleophile (TrOOLi) and an appropriate protecting group, (4) the mild hydrolysis of an α-epoxy nitrile by silica gel on TLC facilitated by hydroxyl-mediated, intramolecular assistance.
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U2 - 10.1021/jo025641m
DO - 10.1021/jo025641m
M3 - Article
C2 - 12492351
AN - SCOPUS:0037184834
SN - 0022-3263
VL - 67
SP - 9443
EP - 9448
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 26
ER -