15358-22-2Relevant academic research and scientific papers
Perchloric acid induced epimerisation of the thevinones: An improved synthesis of 7β-dihydrothevinones
Derrick,Coop,Al-Mousawi,Husbands,Lewis
, p. 7571 - 7576 (2000)
The region above and away from C7 in the orvinols is known to be of particular importance in determining the μ-opioid receptor profile of this important class of opioids. However it has been difficult to explore this site due to the relative inaccessibility of 7β-substituted compounds. Here we report that perchloric acid induced epimerisation of the 7α-ketones (dihydrothevinones) allows considerably improved access to a series of β-ketones (β-dihydrothevinones). The extent of epimerisation of the 7α-ketone is determined by the degree of steric bulk in both the 6,14-bridge and in the ketone side chain. (C) 2000 Elsevier Science Ltd.
Photooxidation of Thebaine. A Route to 14-Hydroxymorphinones and Hydrodibenzofuran Analogs of Methadone.
Lopez, Dolores,Quinoa, Emilio,Riguera, Ricardo
, p. 5727 - 5730 (1994)
The photooxidation of thebaine (1) produces a highly functionalized hydrodibenzofuran 2 via formation of the endoperoxide and a tert-amine radical cation.Photooxidation of the quaternary ammonium salt of thebaine 6, allows the isolation of the endoperoxide 7.Photooxidation of thebaine 1 in acidic medium (TFA), yields 14-hydroxycodeinone salt 3 via the corresponding endoperoxide.
The [4 + 2] Addition of Singlet Oxygen to Thebaine: New Access to Highly Functionalized Morphine Derivatives via Opioid Endoperoxides
Lopez, Dolores,Quinoa, Emilio,Riguera, Ricardo
, p. 4671 - 4678 (2000)
The photooxidation of thebaine (3) with a sun lamp affords two main products: hydrodibenzofuran 10 (major) and benzofuran 11 (minor). The latter compound becomes predominant if a Hg lamp is used instead of a sun lamp. The formation of 10 proceeds via an endoperoxide intermediate that undergoes oxidation at the nitrogen atom. Protection of the nitrogen either by protonation or quaternization prevents its oxidation and thus the photooxidation of 3 in acid media constitutes a one-pot procedure for the preparation of 14-hydroxycodeinone 35. Photooxidation of the thebaine ammonium salt 31 allows the isolation in good yields of the corresponding to thebaine endoperoxide 32. The selective protection and reduction of the keto, aldehyde, and olefinic groups of hydrodibenzofuran 10 allowed the preparation of several diol and keto alcohol derivatives. This is the first report on the use of photooxidation to functionalize thebaine at C(6) and C(14) and also the first on the isolation of opioid endoperoxides.
PROCESS FOR THE SYNTHESIS OF BUPRENORPHINE
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Page/Page column 13, (2021/08/06)
The present invention relates to a novel route of synthesis for the opioid receptor antagonist Buprenorphine or a pharmaceutically acceptable salt thereof, starting from thebaine, wherein the route comprises the reaction of the baine with a dienophile; forming an alkylated reaction product by reaction with a Grignard-reagent; formation of an cyanamide; deprotection of the cyanamide- and the phenolic-oxygen-moiety, wherein the cleavage of one or both groups is performed in the presence of an alkali or alkaline earth sulfide; followed by derivatization with a cyclopropyl-halogen and hydrogenation to yield Buprenorphine.
DEUTERATED COMPOUND AND MEDICAL USE THEREOF
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Paragraph 0017, (2020/01/12)
The present invention relates to a compound represented by formula I and a non-toxic pharmaceutically acceptable salt thereof. In formula (I), R1 is H, CH3 or deuterated methyl (CD3); R2 is CH3 or CH2CH3; R3, R4 and R5 are each independently H or deuterium (D); when R1 is H or CH3, at least one of R3, R4 and R5 is D.
Photoredox Imino Functionalizations of Olefins
Davies, Jacob,Sheikh, Nadeem S.,Leonori, Daniele
supporting information, p. 13361 - 13365 (2017/10/17)
Shown herein is that polyfunctionalized nitrogen heterocycles can be easily prepared by a visible-light-mediated radical cascade process. This divergent strategy features the oxidative generation of iminyl radicals and subsequent cyclization/radical trapping, which allows the effective construction of highly functionalized heterocycles. The reactions proceed efficiently at room temperature, utilize an organic photocatalyst, use simple and readily available materials, and generate, in a single step, valuable building blocks that would be difficult to prepare by other methods.
PROCESS FOR THE PREPARATION OF (S)-2-((4R,4AS, 6R,7AR,12BS)-7,9-DIMETHOXY-1,2,3,4,5,6,7,7A-OCTAHYDRO-4A,7-ETHANO-4, 12-METHANOBENZOFURO[3,2-E] ISOQUINOLIN-6-YL)-3,3-DIMETHYLBUTAN-2-OL
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Paragraph 00142-00147, (2017/05/02)
An invention includes a process for the preparation of (S)-2((4R,4aS,6R,7R,7aR,12bS)-7,9-dimethoxy-1,2,3,4,5,6,7,7a-octahydro-4a,7-ethano-4,12-methanobenzofuro[3,2-e]isoquinolin-6-yl)-3,3-dimethylbutan-2-ol.
PROCESS FOR THE PREPARATION OF OPIOID COMPOUNDS
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Paragraph 0159; 0160, (2015/11/27)
The present invention is directed to a process for the preparation of opioid compounds such as buprenorphine, naltrexone, naloxone, nalbuphone, nalbuphine, and the like.
Industrial process for the preparation of buprenorphine and its intermediates
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Paragraph 0055, (2015/01/18)
There is provided an efficient industrial process for the preparation of 21-cyclopropyl-7a-(2-hydroxy-3,3-dimethyl-2-butyl)-6,14-endo-ethano-6,7,8,14-tetrahydro-oripavine,i.e. buprenorphine of Formula- I in high yield and purity, with enhanced safety and eco-friendly norms. The invention further relates to an improved process for preparation of intermediates thereof in high yield and purity.
Polonovski-type N-demethylation of N-methyl alkaloids using substituted ferrocene redox catalysts
Kok, Gaik B.,Scammells, Peter J.
experimental part, p. 2587 - 2594 (2012/09/22)
Various substituted ferrocenes have been trialed as catalysts in the nonclassical Polonovski reaction for N-demethylation of N-methyl alkaloids. Earlier studies suggest that conditions facilitating a higher ferrocenium ion concentration lead to superior outcomes. In this regard, the bifunctional ferrocene FcCH2CO2H, with electron donor and acceptor moieties in the same molecule, has been shown to be advantageous for use as a catalyst in the N-demethylation of a number of tertiary N-methylamines such as codeine, thebaine, and oripavine. These substrates are readily N-demethylated under mild conditions, employing sub-stoichiometric amounts of the substituted ferrocene at ambient temperature. These reactions are equally efficient in air and may also be carried out in one pot. Georg Thieme Verlag Stuttgart · New York.
