TY - JOUR
T1 - 6-O-demethylation of the thevinols with lithium aluminium hydride
T2 - Selective demethylation of a tertiary alkyl methyl ether in the presence of an aryl methyl ether
AU - Breeden, Simon W.
AU - Coop, Andrew
AU - Husbands, Stephen M.
AU - Lewis, John W.
PY - 1999/11/10
Y1 - 1999/11/10
N2 - In the pursuit of ring-constrained analogues of buprenorphine, we wished to prepare 6-O-demethylated analogues of the thevinols and orvinols. Previously it had been disclosed that lithium aluminum hydride (LAH) in THF containing a chlorinated solvent could achieve this transformation. Here we report the results of our work with LAH in the non-coordinating solvent toluene. In refluxing toluene, the selective 6-O-demethylation of thevinols could be achieved with no 3-O-demethylation being observed. It appears that a C(20)-OH or C(20)-NH2 group is needed on the substrate for this hydrogenolysis to proceed.
AB - In the pursuit of ring-constrained analogues of buprenorphine, we wished to prepare 6-O-demethylated analogues of the thevinols and orvinols. Previously it had been disclosed that lithium aluminum hydride (LAH) in THF containing a chlorinated solvent could achieve this transformation. Here we report the results of our work with LAH in the non-coordinating solvent toluene. In refluxing toluene, the selective 6-O-demethylation of thevinols could be achieved with no 3-O-demethylation being observed. It appears that a C(20)-OH or C(20)-NH2 group is needed on the substrate for this hydrogenolysis to proceed.
UR - http://www.scopus.com/inward/record.url?scp=0032743701&partnerID=8YFLogxK
U2 - 10.1002/(SICI)1522-2675(19991110)82:11<1978::AID-HLCA1978>3.0.CO;2-Q
DO - 10.1002/(SICI)1522-2675(19991110)82:11<1978::AID-HLCA1978>3.0.CO;2-Q
M3 - Article
AN - SCOPUS:0032743701
SN - 0018-019X
VL - 82
SP - 1978
EP - 1980
JO - Helvetica Chimica Acta
JF - Helvetica Chimica Acta
IS - 11
ER -