- Olefin functionalization/isomerization enables stereoselective alkene synthesis
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Despite tremendous efforts aimed at devising methods for stereoselective alkene synthesis, critical challenges are yet to be addressed. Direct access to a diverse range of 1-aryl(boryl)-1-methyl-functionalized tri- and tetrasubstituted trans alkenes, entities that are prevalent in many important molecules, through a catalytic manifold from readily available α-olefin substrates remains elusive. Here, we demonstrate that catalytic amounts of a non-precious N-heterocyclic carbene–Ni(I) complex in conjunction with a sterically bulky base promote site- and trans-selective union of monosubstituted olefins with a wide array of electrophilic reagents to deliver tri- and tetrasubstituted alkenes in up to 92% yield and >98% regio- and stereoselectivity. The protocol is amenable to the preparation of carbon- and heteroatom-substituted C=C bonds, providing distinct advantages over existing transformations. Utility is highlighted through concise stereoselective synthesis of biologically active compounds. [Figure not available: see fulltext.].
- Gutierrez, Osvaldo,Koh, Ming Joo,Liu, Chen-Fei,Martin, Robert T.,Wang, Hongyu,Zhao, Haonan
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p. 674 - 683
(2021/08/06)
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- A method for synthesizing substituted diphenyl derivatives
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The invention relates to a synthesis method of a compound shown in Formula (I). A compound shown in Formula (III) is prepared via reaction of a compound shown in Formula (II) with a phase transfer catalyst, and the compound shown in Formula (I) is prepared via direct hydrolysis of the compound shown in Formula (III).
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Paragraph 0052; 0053
(2017/03/22)
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- 18-20 MEMBER BI-POLYCYCLIC COMPOUNDS
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The invention relates to 18-20 member bi-polycyclic compounds, methods of making these compounds, and methods of using them in treating hyperproliferative disorders (e.g., cancer) and non-malignant tumors; promoting muscle formation; inhibiting muscle degeneration or the loss of muscle mass or muscle function; and myofibers ex vivo.
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- Synthesis of arotinoid acid and temarotene using mixed (Z)-1,2- bis(organylchalcogene)-1-alkene as precursor
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An efficient and novel total synthesis of the two bioactive retinoids temarotene and arotinoid acid (TTNPB) is described. The key steps in this process include the regio and stereoselective hydrotelluration of thioacetylene 9 and Te/Li transmetalation of mixed (Z)-1,2-bis(organylchalcogene)-1-alkene (Z)-3. The subsequent reaction involving the β-phenylthio vinyl lithiated intermediate 10 with dimethyl sulfate gave the (E)-vinyl sulfide 11. The Ni +2 cross-coupling of 11 with the corresponding phenylzinc bromide and p-oxazoline phenylzinc bromide 12 afforded the respective temarotene 2 and retinoid-oxazoline substituted 13. Finally, compound 13 was deprotected with HCl to furnish arotinoid acid (TTNPB) 1.
- Guerrero Jr., Palimécio G.,De Oliveira, Paulo R.,Baroni, Adriano C.M.,Marques, Francisco A.,Labes, Ricardo,Hurtado, Gabriela R.,Dabdoub, Miguel J.
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p. 5302 - 5305
(2012/11/13)
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- Retinoid compounds and their use
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The invention relates to retinoid compounds of the formula (I): wherein V is a hydrophobic group;W is a non-polyenic linker; andX is a polar group comprising a hydrogen bond donor; or a salt thereof, and to the use of such compounds in the control of cell differentiation.
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- A-[(E)-2-(5,6,7,8-TETRAHYDRO-5,5,8,8-TETRAMETHYL-2-NAPTHALENYL)-1-PROPENYL]BENZOIC ACID ANALOGS AND METHOD OF MANUFACTURE AND AND USE THEREOF
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Analogs of 4-[(E)-2-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-napthalenyl)-1 - propenyl]benzoic acid and methods of manufacture and use thereof, such as for use in cancer prevention and treatment.
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Page/Page column 11
(2008/06/13)
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- Programmed cell death (PCD) associated with the stilbene motif of arotinoids: Discovery of novel apoptosis inducer agents possessing activity on multidrug resistant tumor cells
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Considering that the stereochemistry of the C9-C10 alkenyl portion of natural 9-cis-RA, as the one of the olefinic moiety of the previously described isoxazole retinoid 4, seems of particular importance for their apoptotic activity, we prepared a novel class of TTNPB analogues bearing both the cis or trans configuration of the alkenyl portion. The compounds were evaluated in vitro for their cytotoxic and apoptotic activities. We discovered that the cis-TTNPB 9c possesses apoptotic activity comparable with that of the retinoid 4. Moreover, the amino arotinoid 16c showed potent apoptotic activity in HL60 promyelocytic leukemia cells. Interestingly, 16c proved to be a particularly potent apoptosis-inducing agent active in multidrug resistant (MDR) cell lines. Therefore, to the best of our knowledge, 16c may represent the first known aminoarotinoid endowed with potent apoptotic activity in MDR cells. Taken together, these results seem to point out that the cis-stilbene motif of arotinoids may be at least an important feature in conferring cytotoxic and apoptotic activity to this class of compounds. (C) 2000 Elsevier Science Ltd.
- Simoni, Daniele,Roberti, Marinella,Paolo Invidiata, Francesco,Rondanin, Riccardo,Baruchello, Riccardo,Malagutti, Cinzia,Mazzali, Angelica,Rossi, Marcello,Grimaudo, Stefania,Dusonchet, Luisa,Meli, Maria,Raimondi, Maria Valeria,D'Alessandro, Natale,Tolomeo, Manlio
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p. 2669 - 2673
(2007/10/03)
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- Arotinoids, a new class of highly active retinoids
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The synthesis and biological activity of new aromatic retinoids are reported. The most active ones belong to a chemical class of compounds, which we have termed 'arotinoids'. For the compound p-[(E)-2-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl)-propenyl)]-benzoic acid ethyl ester, a therapeutic potency in the antipapilloma test was found which exceeds that of retinoic acid by a factor of 8000, while the concurrently observed toxic hypervitaminosis A effects are only increased by a factor of 800. The structural relationship of the arotinoids with retinoic acid is demonstrated; the arotinoids contain the retinoic acid carbon skeleton in a fixed cisoid geometric conformation.
- Loeliger,Bollag,Mayer
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