- Novel methods of synthesizing naphtho[1,2-c]furan-1,3-dione and benzo[e]isoindole-1,3-dione
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Convenient methods of synthesizing naphtho[1,2-c]furan-1,3-dione and benzo[e]isoindole-1,3-dione from phenylbutyric acid derivatives have been established. Naphtho[1,2-c]furan-1,3-dione and benzo[e]isoindole-1,3-dione were obtained respectively from 4,5-d
- Mizuno, Masahiro,Yamano, Mitsuhisa
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- Preparation method of substituted butyrate derivatives
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The invention discloses a preparation method of substituted butyrate derivatives. The method specifically comprises the following steps: by taking compounds shown in a formula 1, a formula 2 and a formula 3 as raw materials, carrying out an illumination reaction process in the presence of a photocatalyst and a hydrogen transfer catalyst to obtain a target compound shown in a formula I through one-step reaction. The invention discloses a free radical-mediated olefin bifunctional reaction without a cyclopropanation intermediate. The reaction can realize a product which can be obtained through cyclopropanation and cyclopropane ring opening processes traditionally in one step. Meanwhile, the preparation method of the compound is simple, uses cheap and easily available compounds as raw materials, and has the beneficial effects of one-step synthesis, mild reaction conditions, fast reaction, low cost, less generated waste, simple and safe operation, high atom economy, high selectivity, extremely wide substrate applicability, high yield and the like.
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Paragraph 0105-0108
(2020/07/15)
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- Radical-Mediated Strategies for the Functionalization of Alkenes with Diazo Compounds
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One of the most common reactions of diazo compounds with alkenes is cyclopropanation, which occurs through metal carbene or free carbene intermediates. Alternative functionalization of alkenes with diazo compounds is limited, and a methodology for the addition of the elements of Z-CHR2 (with Z = H or heteroatom, and CHR2 originates from N2 CR2) across a carbon-carbon double bond has not been reported. Here we report a novel reaction of diazo compounds utilizing a radical-mediated addition strategy to achieve difunctionalization of diverse alkenes. Diazo compounds are transformed to carbon radicals with a photocatalyst or an iron catalyst through PCET processes. The carbon radical selectively adds to diverse alkenes, delivering new carbon radical species, and then forms products through hydroalkylation by thiol-assisted hydrogen atom transfer (HAT), or forms azidoalkylation products through an iron catalytic cycle. These two processes are highly complementary, proceed under mild reaction conditions, and show high functional group tolerance. Furthermore, both transformations are successfully performed on a gram-scale, and diverse γ-amino esters, γ-amino alcohols, and complex spirolactams are easily prepared with commercially available reagents. Mechanistic studies reveal the plausible pathways that link the two processes and explain the unique advantages of each.
- Su, Yong-Liang,Liu, Geng-Xin,Liu, Jun-Wen,Tram, Linh,Qiu, Huang,Doyle, Michael P.
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supporting information
p. 13846 - 13855
(2020/09/21)
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- RETINOID COMPOUND, PREPARATION METHOD THEREFOR, INTERMEDIATES THEREOF AND APPLICATION THEREOF
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Disclosed are a retinoid compound, a preparation method therefor, intermediates thereof and an application thereof. The retinoid compound I of the present invention has a good tumor growth inhibition rate.
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Paragraph 0132; 0133
(2019/01/29)
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- Synthesis and biological evaluation of 1α,25-dihydroxyvitamin D3 analogues with aromatic side chains attached at C-17
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Two new analogues of the steroid hormone 1?±,25-dihydroxyvitamin D3 with aromatic side chains attached at C-17 were designed to investigate their effects on VDR, HL-60 cell differentiation and tumor cell proliferation. These analogues were prepared by the classical photochemical ring opening approach. After the protection of both the 1α-and 3β-hydroxyl in 1α-hydroxydehydroepiandrosterone with TBS groups, followed by bromination with NBS and debromination in the presence of γ-collidine, the diene intermediate was obtained. Hydrazone formation followed by iodine oxidation gave a vinyl iodide. The aromatic side chain at C-17 was introduced via the Negishi coupling of the resulting intermediate with an in situ generated zinc reagent with the substituted aryl bromide (CD-side chain) in the presence of catalytic amount of Pd(PPh3)4. After the removal of the TBDMS and MOM protective groups, followed by UV irradiation and the subsequent thermal reaction, the 1α,25-(OH)2-D3 analogues with a substituted phenyl ring attached at C-17 to replace the C-20 and C-21 were prepared. In the VDR competitive binding assay, compounds 2 and 3 almost lost their binding ability, and were only 0.01% and 0.015% as potent as the 1α,25-dihydroxyvitamin D3. However, compounds 2 and 3 were as potent as 1α,25-(OH)2-D3 in inducing HL-60 cell differentiation at concentrations of 30, 100, 300, 1000 nM, respectively. Moreover, compounds 2 and 3 exhibited similar or better antiproliferative potency against MCF-7 human breast cancer cells, the IC50 values for analogues 2, 3 and the natural hormone were 7.08, 7.56, and 12.5 μM, respectively.
- Liu, Chao,Zhao, Guo-Dong,Mao, Xinliang,Suenaga, Tsutomu,Fujishima, Toshie,Zhang, Cheng-Mei,Liu, Zhao-Peng
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p. 569 - 575
(2015/02/19)
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- Synthesis and biological evaluation of 1α,25-dihydroxyvitamin D 3 analogues with aromatic side chains attached at C-17
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Two new analogues of the steroid hormone 1α,25-dihydroxyvitamin D3 with aromatic side chains attached at C-17 were designed to investigate their effects on VDR, HL-60 cell differentiation and tumor cell proliferation. These analogues were prepared by the classical photochemical ring opening approach. After the protection of both the 1α- and 3β-hydroxyl in 1α-hydroxydehydroepiandrosterone with TBS groups, followed by bromination with NBS and debromination in the presence of γ-collidine, the diene intermediate was obtained. Hydrazone formation followed by iodine oxidation gave a vinyl iodide. The aromatic side chain at C-17 was introduced via the Negishi coupling of the resulting intermediate with an in situ generated zinc reagent with the substituted aryl bromide (CD-side chain) in the presence of catalytic amount of Pd(PPh3)4. After the removal of the TBDMS and MOM protective groups, followed by UV irradiation and the subsequent thermal reaction, the 1α,25-(OH) 2-D3 analogues with a substituted phenyl ring attached at C-17 to replace the C-20 and C-21 were prepared. In the VDR competitive binding assay, compounds 2 and 3 almost lost their binding ability, and were only 0.01% and 0.015% as potent as the 1α,25-dihydroxyvitamin D3. However, compounds 2 and 3 were as potent as 1α,25-(OH)2-D3 in inducing HL-60 cell differentiation at concentrations of 30, 100, 300, 1000 nM, respectively. Moreover, compounds 2 and 3 exhibited similar or better antiproliferative potency against MCF-7 human breast cancer cells, the IC 50 values for analogues 2, 3 and the natural hormone were 7.08, 7.56, and 12.5 μM, respectively.
- Liu, Chao,Zhao, Guo-Dong,Mao, Xinliang,Suenaga, Tsutomu,Fujishima, Toshie,Zhang, Cheng-Mei,Liu, Zhao-Peng
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p. 569 - 575
(2014/11/07)
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- O- or S- substituted tetrahydronaphthalene derivatives having retinoid and/or retinoid antagonist-like biological activity
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Compounds of the formula where the symbols have the meaning described in the application, have retinoid-like or retinoid antagonist-like biological activity.
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Page column 71
(2010/11/29)
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- Method for inhibiting gene expression promoted by AP1 protein with RAR beta selective retinoids and method for treatment of diseases and conditions with such retinoids
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Retinoid compounds which repress expression of the gene promoted by AP1 protein but which do not significantly activate expression of the genes having RA-responsive elements in their promoter region through RAR alpha and RAR GAMMA receptor subtypes, are u
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- Oxime substituted tetrahydronaphthalene derivatives having retinoid and/or retinoid antagonist-like biological activity
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Compounds of the formula STR1 have retinoid-like or retinoid antagonist-like biological activity.
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- Acetylenes disubstituted with a 5-amino or substituted 5-amino substituted tetrahydronaphthyl group and with an aryl or heteroaryl group having retinoid-like biological activity
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Compounds of the formula STR1 having retinoid like biological activity.
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