Functionalization of the 6,14-bridge of the orvinols. 2. Preparation of 18- and 19-hydroxyl-substituted thevinols and their treatment with benzyl bromide.
The etheno bridge of a thevinone was treated with BH3 and H2O2 to give both the 18- and 19-hydroxyl- substituted thevinols. Selective benzylation of the primary 20-hydroxyl over the 19-hydroxyl was successful; however, benzylation of the 18-hydroxylated product led to a reaction at the more hindered alcohol. Thus, the 6,14-bridge of the Diels-Alder products of thebaine can be hydroxylated, which opens up these positions for further chemical manipulation.
Wu
Huifang
H
Department of Pharmaceutical Sciences, University of Maryland School of Pharmacy, 20 Penn Street, Room 637, Baltimore, Maryland 21201, USA.
Bernard
Denzil
D
Chen
Weibin
W
Strahan
Gary D
GD
Deschamps
Jeffrey R
JR
Parrish
Damon A
DA
Lewis
John W
JW
MacKerell
Alexander D
AD
Coop
Andrew
A
D001593:Benzyl Compounds / Q000737:chemistry*; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D009019:Morphinans / Q000138:chemical synthesis* / Q000737:chemistry; D009294:Narcotics / Q000138:chemical synthesis* / Q000737:chemistry
D001593:Benzyl Compounds; D001952:Bridged-Ring Compounds; D009019:Morphinans; D009294:Narcotics; C105913:thevinone; C038682:benzyl bromide