A Facile Synthesis and Structural Verification of Etorphine and Dihydroetorphine from Codeine

Huang, Xin-Ren; Srimurugan, Sankareswaran; Lee, Gene‐Hsiang; Chen, Chinpiao

doi:10.1002/jccs.201190048

Cited by 4 publications

(1 citation statement)

References 35 publications

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“…[25] Deuterium-labelled versions (6-OCD 3 -20-CD 3À ) of the 20S-and 20R-stereoisomers of etorphine ([ 2 H 6 ]etorphine) and dihydroetorphine ([ 2 H 6 ]dihydroetorphine) were synthesized starting from codeine for the application as internal standard for HPLC and/or gas chromatography-mass spectrometry (GC-MS) investigations applied in blood analyses. [26,27] Dihydroetorphine (DHE), the 18,19-dihydro analogue of etorphine, has no less than seven asymmetric carbon centres (5R,6R,7R,9R,13S,14S,20R) and was first synthesized by Bentley et al in the 1960s. [25] The biologically more active isomer 20Rdihydroetorphine is among the most potent known semisynthetic opiates with up to 12,000-fold higher potency than morphine.…”

Section: Introductionmentioning

confidence: 99%

NMR Analysis of a Series of 6,14‐Ethenomorphinan Derivatives as PET Precursors and Reference Substances**

et al. 2021

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The new semisynthetic oripavine derivative 3-O-trityl-6-Odesmethyl-dihydroetorphine was synthesized from the poppy alkaloid thebaine in a six-step procedure. This compound can be applied as precursor for the radiosynthesis of [6-O-methyl-11 C]-dihydroetorphine ([ 11 C]DHE). We present a detailed description of 1 H and 13 C NMR data of reference standards and precursors for [6-O-methyl-11 C]-and [6-O-(2-[ 18 F]fluoroethyl] orvinols. This includes the complete assignment for 19 oripavine derivatives examined in 1D and 2D NMR experiments. We also investigated the molecular basis for regioselectivity of fluoroalkylation of 3-O-trityl-6-O-desmethyl-phenethyl-orvinol (TDPEO) using computational methods.

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Section: Introductionmentioning

confidence: 99%

NMR Analysis of a Series of 6,14‐Ethenomorphinan Derivatives as PET Precursors and Reference Substances**

et al. 2021

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Asymmetric total synthesis of buprenorphine and dihydroetorphine

Tang

Zhang

Zhao

et al. 2022

Tetrahedron Letters

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Chemoenzymatic Total Synthesis of ent-Oxycodone: Second-, Third-, and Fourth-Generation Strategies

et al. 2019

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Four distinct approaches to ent-oxycodone were designed and accomplished. All rely on the same starting material, the diene diol derived from phenethyl acetate by the whole-cell fermentation with E. coli JM109 (pDTG601A), a strain that overexpresses toluene dioxygenase. The key step in the first-generation approach involves the construction of the C-9/C-14 bond by a SmI2-mediated cyclization of a keto aldehyde. The second-generation design relies on the use of the Henry reaction to accomplish this task. In both of these syntheses, Parker’s cyclization was employed to construct the D-ring. The third-generation synthesis provides an improvement over the second in that the nitrogen atom at C-9 is introduced by azidation of the C-9/C-10 olefin, followed by reduction and lactam formation between the C-9 amine and the Fukuyama-type lactone. Finally, the fourth generation takes advantage of the keto–nitrone reductive coupling to generate the C-9/C-14 linkage. The four generations of the total syntheses of ent-oxycodone were accomplished in 13, 18, 16, and 11 operations (19, 23, 24, and 18 steps), respectively. Experimental and spectral data are provided for all new compounds.

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A Facile Synthesis and Structural Verification of Etorphine and Dihydroetorphine from Codeine

Cited by 4 publications

References 35 publications

NMR Analysis of a Series of 6,14‐Ethenomorphinan Derivatives as PET Precursors and Reference Substances**

NMR Analysis of a Series of 6,14‐Ethenomorphinan Derivatives as PET Precursors and Reference Substances**

Asymmetric total synthesis of buprenorphine and dihydroetorphine

Chemoenzymatic Total Synthesis of ent-Oxycodone: Second-, Third-, and Fourth-Generation Strategies

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