Biomimetic synthesis of acid-sensitive (-)-caparrapi oxide and (+)-8-epicaparrapi oxide induced by artificial cyclases.
[reaction: see text] Asymmetric total syntheses of acid-sensitive (-)-caparrapi oxide (1) and (+)-8-epicaparrapi oxide (2) from farnesol (9) were achieved using Sharpless-Katsuki epoxidation and Lewis acid-assisted chiral Bronsted acid (chiral LBA)-induced polyene cyclization as key steps. Furthermore, (-)-1 could be directly synthesized from (S)-nerolidol (3) and (R)-LBA with 88% ds by reagent control which overcame substrate control, while (-)-2 was obtained from (R)-3 and (R)-LBA with >99% ds by the double-asymmetric induction.
Uyanik
Muhammet
M
Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan.
Ishibashi
Hideaki
H
Ishihara
Kazuaki
K
Yamamoto
Hisashi
H
D000143:Acids / Q000737:chemistry*; D004798:Enzymes / Q000378:metabolism*; D018716:Molecular Mimicry; D015394:Molecular Structure; D010087:Oxides / Q000138:chemical synthesis*; D012717:Sesquiterpenes / Q000138:chemical synthesis*; D013057:Spectrum Analysis; D013237:Stereoisomerism
C507272:8-epicaparrapi oxide; D000143:Acids; D004798:Enzymes; D010087:Oxides; D012717:Sesquiterpenes; C507273:caparrapi oxide; C037055:nerolidol