- Preparation method and application of acetophenone derivative
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The invention discloses a preparation method of an acetophenone derivative. The method comprises the following steps: weighing 7-9 parts by weight of 1-bromine-4-methyl benzene, putting the 1-bromine-4-methyl benzene into a reaction kettle, and adding 7-11 parts by weight of DMSO to completely dissolve the 1-bromine-4-methyl benzene; respectively weighing 4-6 parts of tetrakis(triphenylphosphine)palladium, 15-19 parts of p-bromotoluene and 27-31 parts of 1, 8-diazabicyclo undec-7-ene, dissolving the components above in 14-16 parts of DMSO, adding the mixture into the reaction kettle, and stirring the reaction liquid at 33-38 DEG C for 20-28 hours; weighing 0.3-0.5 part of 3-(p-tolyl)propionic acid and 0.3-0.5 part of di-tert-butyl peroxide and putting the components into a reaction kettle, adding 14-16 parts of cyclohexane, stirring the reaction system for 16-18 hours in a nitrogen atmosphere at 98-102 DEG C, and taking samples regularly by removing a sampler every two hours during the stirring process; and after the reaction is finished, extracting the reaction liquid with ethyl acetate for three times to obtain the product. According to the invention, tetrakis(triphenylphosphine)palladium is adopted as an important means for efficiently constructing a compound through inert hydrocarbon activation, and the used metal catalyst is low in price and small in the harm to the environment.
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Paragraph 0036; 0045; 0049; 0051; 0055; 0057; 0060
(2021/06/06)
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- Selective catalytic synthesis of α-alkylated ketones and β-disubstituted ketones via acceptorless dehydrogenative cross-coupling of alcohols
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Herein, a phosphine-free pincer ruthenium(III) catalyzed β-alkylation of secondary alcohols with primary alcohols to α-alkylated ketones and two different secondary alcohols to β-branched ketones are reported. Notably, this transformation is environmentally benign and atom efficient with H2O and H2 gas as the only byproducts. The protocol is extended to gram-scale reaction and for functionalization of complex vitamin E and cholesterol derivatives.
- Bhattacharyya, Dipanjan,Sarmah, Bikash Kumar,Nandi, Sekhar,Srivastava, Hemant Kumar,Das, Animesh
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supporting information
p. 869 - 875
(2021/02/06)
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- MODULATORS OF HSD17B13 AND METHODS OF USE THEREOF
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The disclosure relates to compounds and pharmaceutical compositions capable of modulating the hydroxysteroid 17-beta dehydrogenase (HSD17B) family member proteins including inhibiting the HSD17B member proteins, e.g. HSD17B13. The disclosure further relates to methods of treating liver diseases, disorders, or conditions with the compounds and pharmaceutical compositions disclosed herein, in which the HSD17B family member protein plays a role.
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Paragraph 0677
(2021/01/23)
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- Ruthenium-Catalyzed α-Alkylation of Ketones Using Secondary Alcohols to β-Disubstituted Ketones
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An assortment of aromatic ketones was successfully functionalized with a variety of unactivated secondary alcohols that serve as alkylating agents, providing β-disubstituted ketone products in good to excellent yields. Remarkably, challenging substrates such as simple acetophenone derivatives are effectively alkylated under this ruthenium catalysis. The substituted cyclohexanol compounds displayed product-induced diastereoselectivity. Mechanistic studies indicate the involvement of the hydrogen-borrowing pathway in these alkylation reactions. Notably, this selective and catalytic C-C bond-forming reaction requires only a minimal load of catalyst and base and produces H2O as the only byproduct, making this protocol attractive and environmentally benign.
- Thiyagarajan, Subramanian,Vijaya Sankar, Raman,Gunanathan, Chidambaram
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supporting information
p. 7879 - 7884
(2020/11/02)
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- Iron-Catalyzed Oxyalkylation of Terminal Alkynes with Alkyl Iodides
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A general oxyalkylation of terminal alkynes enabled by iron catalysis has been developed. Primary and secondary alkyl iodides acted as the alkylating reagents and afforded a range of α-alkylated ketones under mild reaction conditions. Acetyl tert-butyl peroxide (TBPA) was used as the radical relay precursor, providing the initiated methyl radical to start the radical relay process. Preliminary mechanistic studies were conducted, and late-stage functionalizations of natural product derivatives were performed.
- Deng, Weili,Ye, Changqing,Li, Yajun,Li, Daliang,Bao, Hongli
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supporting information
p. 261 - 265
(2019/01/10)
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- Catalytic Cross-Coupling of Secondary Alcohols
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Herein, an unprecedented ruthenium(II) catalyzed direct cross-coupling of two different secondary alcohols to β-disubstituted ketones is reported. Cyclic, acylic, symmetrical, and unsymmetrical secondary alcohols are selectively coupled with aromatic benzylic secondary alcohols to provide ketone products. A single catalyst oxidizes both secondary alcohols to provide selectively β-disubstituted ketones to broaden the scope of this catalytic protocol. Number of bond activation and bond formation reactions occur in selective sequence via amine-amide metal-ligand cooperation operative in Ru-MACHO catalyst. The product-induced diastereoselectivity was also observed. Kinetic and deuterium labeling experiments suggested that the aliphatic secondary alcohols undergo oxidation reaction faster than benzylic secondary alcohols, selectively assimilating to provide the cross-coupled products. Reactions are sensitive to steric hindrance. This new C-C bond forming methodology requires low catalyst load and catalytic amount of base. Notably, the reaction produces H2 and H2O as the only byproducts making the protocol greener, atom economical and environmentally benign.
- Thiyagarajan, Subramanian,Gunanathan, Chidambaram
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supporting information
p. 3822 - 3827
(2019/04/09)
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- Ruthenium-Catalyzed Direct Cross-Coupling of Secondary Alcohols to β-Disubstituted Ketones
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The β-disubstituted ketone functionality is prevalent in biologically active compounds and in pharmaceuticals. A ruthenium-catalyzed direct synthesis of β-disubstituted ketones by cross-coupling of two different secondary alcohols is reported. This new protocol was applied to the synthesis of variety of β-disubstituted ketones from various cyclic, acyclic, symmetrical, and unsymmetrical secondary alcohols. An amine-amide metal-ligand cooperation in a Ru catalyst facilitates the activation and formation of covalent bonds in selective sequences to provide the products. Kinetic and deuterium-labeling experiments suggested that aliphatic alcohols oxidize faster than benzylic secondary alcohols. A plausible mechanism is proposed on the basis of mechanistic and kinetic studies. Water and H 2 are the only byproducts from this selective cross-coupling of secondary alcohols. 1 Introduction 2 Catalytic Self-or Cross-Coupling of Alcohols and Selectivity Challenges 3 Recent Developments in the Synthesis of β-Disubstituted Ketones 4 Scope of Ruthenium-Catalyzed Cross-Couplings of Secondary Alcohols 5 Mechanistic Studies and Proposed Mechanism 6 Conclusion.
- Gunanathan, Chidambaram,Thiyagarajan, Subramanian
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p. 2027 - 2034
(2019/11/05)
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- Iron-Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides
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An iron-catalyzed oxyalkylation of alkynes with alkyl peroxides as the alkylating reagents has been investigated. Alkyl peroxides are readily available from aliphatic acids and serve simultaneously as the alkylating reagents and internal oxidants. Primary, secondary, and tertiary alkyl groups of aliphatic acids were readily incorporated into C?C triple bonds and diverse α-alkylated ketones were synthesized. Mechanism studies revealed that this reaction involves highly reactive alkyl free radicals. A unique equilibrium between lauric acid and water catalyzed by the iron(III) catalyst was observed.
- Zhu, Xiaotao,Ye, Changqing,Li, Yajun,Bao, Hongli
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supporting information
p. 10254 - 10258
(2017/08/07)
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- Peroxide promoted tunable decarboxylative alkylation of cinnamic acids to form alkenes or ketones under metal-free conditions
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A tunable decarboxylative alkylation of cinnamic acids with alkanes was developed to form alkenes or ketones under transition metal-free conditions. In the presence of DTBP or DTBP/TBHP, the reaction gave alkenes and ketones respectively via a radical mechanism in moderate to good yields. This journal is
- Ji, Jing,Liu, Ping,Sun, Peipei
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supporting information
p. 7546 - 7549
(2015/05/04)
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- Type II Photoelimination from α-Cycloalkylacetophenones and a Polystyrene-Bound Analogue
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In order to evaluate the effects of polymer binding on photoreactivity and other photochemical properties, we have synthesized α-cyclohexyl-p-methylacetophenone (I), α-cyclopentylacetophenone (II), and an analogue bound to insoluble polystyrene beads (P-I).All undergo type II photoelimination and are effective in energy transfer to an added quencher, trans-stilbene.Quantitative comparisons show that the polymer binding has little effect upon the photoreactivity as long as the polymer is in a swelling solvent, such as pentane, which allows the necessary molecular flexibility.The efficiency of energy transfer is somewhat reduced upon polymer binding.
- Wamser, Carl C.,Wagner, William R.
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p. 7232 - 7234
(2007/10/02)
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