6-O-demethylation of the thevinols with lithium aluminium hydride: Selective demethylation of a tertiary alkyl methyl ether in the presence of an aryl methyl ether

S W  Breeden; A  Coop; S M  Husbands; J W  Lewis

6-O-demethylation of the thevinols with lithium aluminium hydride: Selective demethylation of a tertiary alkyl methyl ether in the presence of an aryl methyl ether

S W Breeden, A Coop, S M Husbands, J W Lewis

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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(2O)-NH2 group is needed on the substrate for this hydrogenolysis to proceed.

Original language	English
Pages (from-to)	1978-1980
Number of pages	3
Journal	HELVETICA CHIMICA ACTA
Volume	82
Issue number	11
Publication status	Published - 1999

Cite this

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title = "6-O-demethylation of the thevinols with lithium aluminium hydride: Selective demethylation of a tertiary alkyl methyl ether in the presence of an aryl methyl ether",

abstract = "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(2O)-NH2 group is needed on the substrate for this hydrogenolysis to proceed.",

author = "Breeden, {S W} and A Coop and Husbands, {S M} and Lewis, {J W}",

year = "1999",

language = "English",

volume = "82",

pages = "1978--1980",

journal = "HELVETICA CHIMICA ACTA",

issn = "0018-019X",

publisher = "Verlag Helvetica Chimica Acta AG",

number = "11",

}

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, S W

AU - Coop, A

AU - Husbands, S M

AU - Lewis, J W

PY - 1999

Y1 - 1999

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(2O)-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(2O)-NH2 group is needed on the substrate for this hydrogenolysis to proceed.

M3 - Article

SN - 0018-019X

VL - 82

SP - 1978

EP - 1980

JO - HELVETICA CHIMICA ACTA

JF - HELVETICA CHIMICA ACTA

IS - 11

ER -