23758-27-2Relevant academic research and scientific papers
Sequential Ketene Generation from Dioxane-4,6-dione-keto-dioxinones for the Synthesis of Terpenoid Resorcylates
Elliott, Daniel C.,Ma, Tsz-Kan,Selmani, Aymane,Cookson, Rosa,Parsons, Philip J.,Barrett, Anthony G. M.
, p. 1800 - 1803 (2016)
Trapping of the ketene generated from the thermolysis of 2-methyl-2-phenyl-1,3-dioxane-4,6-dione-keto-dioxinone at 50°C with primary, secondary, or tertiary alcohols gave the corresponding dioxinone β-keto-esters in good yield under neutral conditions. Th
CANNABINOID DERIVATIVES
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Paragraph 0136, (2021/01/23)
The present invention provides cannabinoid derivatives, a pharmaceutical composition comprising said derivative and a method of using said derivatives in treating or preventing a disease associated with cannabinoid receptors. The claimed cannabinoid derivatives are described by the following formula or an enantiomer, diastereomer, racemate, tautomer, or metabolite thereof, or a pharmaceutically acceptable salt, solvate or hydrate of the compound.
CANNABINOID DERIVATIVES
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Paragraph 0133, (2021/02/12)
This disclosure relates generally to cannabinoid derivatives of the following structure, pharmaceutical compositions comprising them, and methods of treating or preventing diseases associated with cannabinoid receptors using said compounds.
Enantioselective Cu-catalyzed 1,4-additions of organozinc and Grignard reagents to enones: Exceptional performance of the hydrido-phosphite-ligand BIFOP-H
Brüllingen, Eric,Neud?rfl, J?rg-Martin,Goldfuss, Bernd
supporting information, p. 4787 - 4799 (2019/03/26)
Enantioselective Cu(I),(II)-(i.e. CuCl, CuCl2, Cu(OTf)2)-catalyzed 1,4-additions of organozinc, i.e. (Et, Me)2Zn, and Grignard reagents, i.e. (Et, Me)MgBr, to chalcone, cyclohexenone and chromone are studied, employing fencholate-based phosphorus ligands, e.g. biphenyl-2,2′-bisfenchyl hydrido phosphite = BIFOP-H. The CuCl·BIFOP-H-catalyzed 1,4-addition of Et2Zn to chalcone yields up to 93% and 99% ee, exceeding established BINOL- and TADDOL-based phosphoramidite ligands. Remarkably, CuCl performs better in 1,4-additions to chalcone (CuCl: 76% ee; Cu(OTf)2: 49% ee; CuCl2: 42% ee) while Cu(OTf)2 performs better in 1,4-additions to cyclohexenone (Cu(OTf)2: 65% ee; CuCl: 20% ee). The computation of the reaction pathway is done for the CuI-catalyzed 1,4-addition to chalcone (CuII will be in situ reduced to CuI by a reagent, TPSS-D3(BJ)/def2-TZVP//B3LYP-D3(BJ)/def2-SVP) for six different model ligands, i.e. (MeO)2P-X (X = H, F, Me, OMe, NMe2 and PMe3). Origins of enantioselectivities are analyzed (M06-2X-D3/def2-TZVP//B3LYP-D3(BJ)/def2-SVP) for transition structures of the 1,4-methylation of chalcone with the Cu·BIFOP-H catalyst and explain the experimentally observed (R)-enantiomer's preference.
Guanidine–Copper Complex Catalyzed Allylic Borylation for the Enantioconvergent Synthesis of Tertiary Cyclic Allylboronates
Ge, Yicen,Cui, Xi-Yang,Tan, Siu Min,Jiang, Huan,Ren, Jingyun,Lee, Nicholas,Lee, Richmond,Tan, Choon-Hong
supporting information, p. 2382 - 2386 (2019/02/01)
An enantioconvergent synthesis of chiral cyclic allylboronates from racemic allylic bromides was achieved by using a guanidine–copper catalyst. The allylboronates were obtained with high γ/α regioselectivities (up to 99:1) and enantioselectivities (up to 99 % ee), and could be further transformed into diverse functionalized allylic compounds without erosion of optical purity. Experimental and DFT mechanistic studies support an SN2′ borylation process catalyzed by a monodentate guanidine–copper(I) complex that proceeds through a special direct enantioconvergent transformation mechanism.
Lewis acids promoted 3 + 2 cycloaddition of oxaziridines and cyclic allylic alcohols through carbonyl imine intermediates
Zhao, Erbao,Zhou, Feilong,Zhao, Yujun
, p. 4282 - 4293 (2019/04/30)
Syntheses of isoxazolidines through the carbonyl imine intermediates are currently limited to monosubstituted olefin substrates. Herein, we reported syntheses of novel bicyclic isoxazolidine-containing compounds through 1,3-dipolar cycloaddition reactions
Aerobic oxidation of the C-H bond under ambient conditions using highly dispersed Co over highly porous N-doped carbon
Nie, Renfeng,Chen, Jingwen,Chen, Minda,Qi, Zhiyuan,Goh, Tian-Wei,Ma, Tao,Zhou, Lin,Pei, Yuchen,Huang, Wenyu
, p. 1461 - 1466 (2019/03/26)
Highly dispersed Co sites in highly porous N-doped carbon (Co-NC) were synthesized by high-temperature pyrolysis of Zn/Co bimetallic zeolitic imidazolate framework-8 (CoxZn100-x-ZIF). Wide characterization indicated that the pyrolysis atmosphere and temperature play crucial roles in the metal dispersion and pore structure of the resulting materials. A hydrogen treatment at elevated temperatures is found to favour the Zn volatilization and restrict the pore shrinkage of the ZIF precursor, thus yielding efficient catalysts with highly dispersed Co, a high surface area (1090 m2 g-1) and pore volume (0.89 cm3 g-1). When used as a catalyst for aerobic oxidation of ethylbenzene (EB), Co1Zn99-ZIF-800-H2 contributes to 98.9% EB conversion and 93.1% ketone selectivity under mild conditions (60 °C, 1 atm O2), which is 41.3 times more active in comparison to the ZIF-67-derived Co catalyst. Co-NC is stable and could be reused four times without obvious deactivation. This catalyst displays good chemoselectivity to the corresponding ketones when using a broad scope of hydrocarbon compounds.
Chemo-Enzymatic Oxidative Rearrangement of Tertiary Allylic Alcohols: Synthetic Application and Integration into a Cascade Process
Brenna, Elisabetta,Crotti, Michele,De Pieri, Matteo,Gatti, Francesco G.,Manenti, Gabriele,Monti, Daniela
supporting information, p. 3677 - 3686 (2018/06/04)
A chemo-enzymatic catalytic system, comprised of Bobbitt's salt and laccase from Trametes versicolor, allowed the [1,3]-oxidative rearrangement of endocyclic allylic tertiary alcohols into the corresponding enones under an Oxygen atmosphere in aqueous media. The yields were in most cases quantitative, especially for the cyclopent-2-en-1-ol or the cyclohex-2-en-1-ol substrates without an electron withdrawing group (EWG) on the side chain. Transpositions of macrocyclic alkenols or tertiary alcohols bearing an EWG on the side chain were instead carried out in acetonitrile by using an immobilized laccase preparation. Dehydro-Jasmone, dehydro-Hedione, dehydro-Muscone and other fragrance precursors were directly prepared with this procedure, while a synthetic route was developed to easily transform a cyclopentenone derivative into trans-Magnolione and dehydro-Magnolione. The rearrangement of exocyclic allylic alcohols was tested as well, and a dynamic kinetic resolution was observed: α,β-unsaturated ketones with (E)-configuration and a high diastereomeric excess were synthesized. Finally, the 2,2,6,6-tetramethyl-1-piperidinium tetrafluoroborate (TEMPO+BF4?)/laccase catalysed oxidative rearrangement was combined with the ene-reductase/alcohol dehydrogenase cascade process in a one-pot three-step synthesis of cis or trans 3-methylcyclohexan-1-ol, in both cases with a high optical purity. (Figure presented.).
Lithium-Catalyzed Thiol Alkylation with Tertiary and Secondary Alcohols: Synthesis of 3-Sulfanyl-Oxetanes as Bioisosteres
Croft, Rosemary A.,Mousseau, James J.,Choi, Chulho,Bull, James A.
supporting information, p. 818 - 821 (2017/12/26)
3-Sulfanyl-oxetanes are presented as promising novel bioisosteric replacements for thioesters or benzyl sulfides. From oxetan-3-ols, a mild and inexpensive Li catalyst enables chemoselective C?OH activation and thiol alkylation. Oxetane sulfides are formed from various thiols providing novel motifs in new chemical space and specifically as bioisosteres for thioesters due to their similar shape and electronic properties. Under the same conditions, various π-activated secondary and tertiary alcohols are also successful. Derivatization of the oxetane sulfide linker provides further novel oxetane classes and building blocks. Comparisons of key physicochemical properties of the oxetane compounds to selected carbonyl and methylene analogues indicate that these motifs are suitable for incorporation into drug discovery efforts.
(Guanidine)copper Complex-Catalyzed Enantioselective Dynamic Kinetic Allylic Alkynylation under Biphasic Condition
Cui, Xi-Yang,Ge, Yicen,Tan, Siu Min,Jiang, Huan,Tan, Davin,Lu, Yunpeng,Lee, Richmond,Tan, Choon-Hong
supporting information, p. 8448 - 8455 (2018/06/22)
Highly enantioselective allylic alkynylation of racemic bromides under biphasic condition is furnished in this report. This approach employs functionalized terminal alkynes as pro-nucleophiles and provides 6- and 7-membered cyclic 1,4-enynes with high yields and excellent enantioselectivities (up to 96% ee) under mild conditions. Enantioretentive derivatizations highlight the synthetic utility of this transformation. Cold-spray ionization mass spectrometry (CSI-MS) and X-ray crystallography were used to identify some catalytic intermediates, which include guanidinium cuprate ion pairs and a copper-alkynide complex. A linear correlation between the enantiopurity of the catalyst and reaction product indicates the presence of a copper complex bearing a single guanidine ligand at the enantio-determining step. Further experimental and computational studies supported that the alkynylation of allylic bromide underwent an anti-SN2′ pathway catalyzed by nucleophilic cuprate species. Moreover, metal-assisted racemization of allylic bromide allowed the reaction to proceed in a dynamic kinetic fashion to afford the major enantiomer in high yield.
