- H2O2-mediated room temperature synthesis of 2-arylacetophenones from arylhydrazines and vinyl azides in water
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An environmentally benign, cost-efficient and practical methodology for the room temperature synthesis of 2-arylacetophenones in water has been discovered. The facile and efficient transformation involves the oxidative radical addition of arylhydrazines with α-aryl vinyl azides in the presence of H2O2 (as a radical initiator) and PEG-800 (as a phase-transfer catalyst). From the viewpoint of green chemistry and organic synthesis, the present protocol is of great significance because of using cheap, non-toxic and readily available starting materials and reagents as well as amenability to gram-scale synthesis, which provides an attractive strategy to access 2-arylacetophenones.
- Luo, Mengqiang,Zhang, Yaohong,Fang, Ping,Li, Yan,Qi, Chenze,Li, Yong,Shen, Runpu,Cheng, Kai,Wang, Hai
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supporting information
p. 630 - 635
(2022/02/01)
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- 1,2-Aryl Migration Induced by Amide C?N Bond-Formation: Reaction of Alkyl Aryl Ketones with Primary Amines Towards α,α-Diaryl β,γ-Unsaturated γ-Lactams
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Rearrangement reactions incorporated into cascade reactions play an important role in rapidly increasing molecular complexity from readily available starting materials. Reported here is a Cu-catalyzed cascade reaction of α-(hetero)aryl-substituted alkyl (hetero)aryl ketones with primary amines that incorporates an unusual 1,2-aryl migration induced by amide C?N bond formation to produce a class of structurally novel α,α-diaryl β,γ-unsaturated γ-lactams in generally good-to-excellent yields. This cascade reaction has a broad substrate scope with respect to primary amines, allows a wide spectrum of (hetero)aryl groups to smoothly undergo 1,2-migration, and tolerates electronically diverse α-substituents on the (hetero)aryl ring of the ketones. Mechanistically, this 1,2-aryl migration may stem from the intramolecular amide C?N bond formation which induces nucleophilic migration of the aryl group from the acyl carbon center to the electrophilic carbon center that is conjugated with the resulting iminium moiety.
- Hu, Rong,Tao, Yigao,Zhang, Xiaofeng,Su, Weiping
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supporting information
p. 8425 - 8430
(2021/03/16)
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- Iron-Catalyzed Enantioselective Radical Carboazidation and Diazidation of α,β-Unsaturated Carbonyl Compounds
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Azidation of alkenes is an efficient protocol to synthesize organic azides which are important structural motifs in organic synthesis. Enantioselective radical azidation, as a useful strategy to install a C-N3 bond, remains challenging due to the inherently instability and unique structure of radicals. Here, we disclose an efficient enantioselective radical carboazidation and diazidation of α,β-unsaturated ketones and amides catalyzed by chiral N,N′-dioxide/Fe(OTf)2 complexes. An array of substituted alkenes was transformed to the corresponding α-azido carbonyl derivatives in good to excellent enantioselectivities, benefiting the preparation of chiral α-amino ketones, vicinal amino alcohols, and vicinal diamines. Control experiments and mechanistic studies proved the radical pathway in the reaction process. The DFT calculations showed that the azido transferred to the radical intermediate via an intramolecular five-membered transition state with the internal nitrogen of the Fe-N3 species.
- Dong, Shunxi,Feng, Xiaoming,He, Jun,Liu, Wen,Liu, Xiaohua,Pu, Maoping,Wu, Yun-Dong,Zhang, Tinghui
-
supporting information
p. 11856 - 11863
(2021/08/16)
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- Preparation method of aryl ketone
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The invention discloses a preparation method of aryl ketone. The preparation method comprises the following steps: mixing a phenyl epoxy compound, aryl trifluoromethanesulfonate, a phosphine ligand, a nickel source, alkali and an organic solvent, and conducting reacting in one step under the protection of inert gas to generate aryl ketone. The preparation method disclosed by the invention is simple in process, mild in conditions and low in cost, and paves a way for large-scale industrial production application, such as drug synthesis or natural product synthesis application, of aryl ketone serving as an important organic reaction intermediate.
- -
-
Paragraph 0053-0058
(2021/10/11)
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- Palladium-catalyzed synthesis of α-aryl acetophenones from styryl ethers and aryl diazonium saltsviaregioselective Heck arylation at room temperature
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Preparation of α-aryl acetophenones from styryl ethers and aryldiazonium salts is described. The reaction is catalyzed by palladium acetate at room temperature in the absence of ligand and base. The developed method is highly attractive in terms of reaction conditions, substrate scope, functional group tolerance and yields. Synthetic applications of the present method are demonstrated by preparing α-aryl indoles and 3-aryl isocoumarin from styryl ethers.
- Kandasamy, Jeyakumar,Lee, Yong Rok,Singh, Adesh Kumar,Venkatesh, Rapelly
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supporting information
p. 7832 - 7837
(2021/09/28)
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- Ruthenium(II)-Catalyzed Cross-Coupling of Benzoyl Formic Acids with Toluenes: Synthesis of 2-Phenylacetophenones
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Herein, we report a direct method to synthesize 2-phenylacetophenone through a ruthenium(II)-catalyzed cross-coupling reaction between acyl and benzyl radical. The various derivatives of 2-phenylacetophenone were prepared easily in moderate to good yields. These reactions provide a straightforward pathway to synthesize a variety of ketones bearing various functional groups.
- Chen, Yujie,Dai, Chenyang,Huang, Zhibin,Jiang, Yaqiqi,Shu, Sai,Yang, Shan,Zhao, Yingsheng
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p. 2955 - 2961
(2021/07/22)
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- Versatile and base-free copper-catalyzed α-arylations of aromatic ketones using diaryliodonium salts
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A ligand and base-free copper catalyzed synthetic method for the efficient α-arylation of aromatic ketones is described. In order to avoid strong bases, ketone-derived silyl enol ethers were employed. Their reaction with diaryliodonium salts as aryl source provided the intermolecular C–C coupling displaying good functional group tolerance and requiring low catalyst loading.
- Bouquin, Maxime,Jaroschik, Florian,Taillefer, Marc
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- Palladium-catalyzed denitrative α-arylation of ketones with nitroarenes
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The palladium-catalyzed α-arylation of ketones with readily available nitroarenes and nitroheteroarenes provides access to useful α-aryl and α-heteroaryl ketones. The use of the Pd/ BrettPhos catalysts was critical to achieve high efficiency for these transformations, whereas other catalysts led to decreased yields or no conversions. The intramolecular type substrate was also applied in this methodology and gave a chromone derivative. Polyaromatic carbonyl compounds can be easily obtained by multicomponent tandem reactions, via nucleophilic aromatic substitution (SNAr) or cross-coupling reaction followed by this denitrative arylation. Kinetic experiments show that the electronic effect of nitrobenzenes has a greater effect on the reaction rate than the electronic effect of ketones.
- Li, Zhirong,Peng, Yonggang,Wu, Tao
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supporting information
(2021/02/16)
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- The organocatalytic enantiodivergent fluorination of β-ketodiaryl-phosphine oxides for the construction of carbon-fluorine quaternary stereocenters
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Commercially available cinchona alkaloids that can catalyze the enantiodivergent fluorination of β-ketodiarylphosphine oxides were developed to construct carbon-fluorine quaternary stereocenters. This protocol features a wide scope of substrates and excellent enantioselectivities, and it is scalable.
- Xie, Shaolei,He, Zhi-Juan,Zhang, Ling-Hui,Huang, Bo-Lun,Chen, Xiao-Wei,Zhan, Zong-Song,Zhang, Fu-Min
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p. 2069 - 2072
(2021/03/01)
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- Aerobic oxygenation of α-methylene ketones under visible-light catalysed by a CeNi3complex with a macrocyclic tris(salen)-ligand
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A hetero-tetranuclear CeNi3 complex with a macrocyclic ligand catalysed the aerobic oxygenation of a methylene group adjacent to a carbonyl group under visible-light radiation to produce the corresponding α-diketones. The visible-light induced homolysis of the Ce-O bond of a bis(enolate) intermediate is proposed prior to aerobic oxygenation.
- Fujiwara, Sakiko,Kon, Yoshihiro,Mashima, Kazushi,Nagae, Haruki,Okuda, Jun,Sakamoto, Kazutaka,Sato, Kazuhiko,Schindler, Tobias
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supporting information
p. 11169 - 11172
(2021/11/04)
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- A copper-catalyzed insertion of sulfur dioxide: Via radical coupling
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A copper-catalyzed three-component reaction of O-acyl oximes, DABCO·(SO2)2, and 2H-azirines under mild conditions has been achieved. This protocol provides an efficient route for the construction of various tetrasubstituted β-sulfonyl N-unprotected enamines in moderate to good yields with excellent stereoselectivity and regioselectivity. Notably, this method represents a rare example of 2H-azirines as useful synthons for β-functionalized N-unprotected enamines. Preliminary mechanistic studies indicate that the reaction proceeds through coupling of a sulfonyl radical and α-carbon radical via copper-catalyzed ring-opening C-C bond cleavage of O-acyl oxime and C-N bond cleavage of 2H-azirine with the insertion of sulfur dioxide.
- Zhang, Jun,Yang, Min,Liu, Jin-Biao,He, Fu-Sheng,Wu, Jie
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supporting information
p. 3225 - 3228
(2020/03/23)
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- Blue Light Promoted Difluoroalkylation of Aryl Ketones: Synthesis of Quaternary Alkyl Difluorides and Tetrasubstituted Monofluoroalkenes
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A facile and cost-effective method for the preparation of fluoroalkylated compounds has been described by the direct photoexcitation of halofluoroalkanes with blue light absorptivity, enabling the difluoroalkylation of aryl ketones. The methodology has provided an efficient, mild, and catalyst-free synthetic method for quaternary difluoroalkylated arenes and tetrasubstituted monofluoroalkenes.
- Li, Kangkui,Chen, Jingchao,Yang, Chunhui,Zhang, Keyang,Pan, Chunxiang,Fan, Baomin,Fan, Baomin
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supporting information
p. 4261 - 4265
(2020/06/04)
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- Thianthrenation-enabled α-arylation of carbonyl compounds with arenes
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The Pd-catalyzed α-arylation of carbonyl compounds with simple arenes enabled by site-selective thianthrenation has been demonstrated. This onepot process using thianthrenium salts as the traceless arylating reagents features mild conditions and a broad substrate scope. In addition, this protocol could also tolerate the heterocyclic carbonyl compounds and complex bioactive molecules, which is appealing for medicinal chemistry.
- Huang, Yu-Hao,Nie, Xiao-Xue,Wang, Peng
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supporting information
p. 7716 - 7720
(2020/11/02)
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- Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids
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As a key element in the construction of complex organic scaffolds, the formation of C?C bonds remains a challenge in the field of synthetic organic chemistry. Recent advancements in single-electron chemistry have enabled new methods for the formation of various C?C bonds. Disclosed herein is the development of a novel single-electron reduction of acyl azoliums for the formation of ketones from carboxylic acids. Facile construction of the acyl azolium in situ followed by a radical–radical coupling was made possible merging N-heterocyclic carbene (NHC) and photoredox catalysis. The utility of this protocol in synthesis was showcased in the late-stage functionalization of a variety of pharmaceutical compounds. Preliminary investigations using chiral NHCs demonstrate that enantioselectivity can be achieved, showcasing the advantages of this protocol over alternative methodologies.
- Betori, Rick C.,Davies, Anna V.,Fitzpatrick, Keegan P.,Scheidt, Karl A.
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supporting information
p. 9143 - 9148
(2020/03/30)
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- Ni/Ti Dual Catalytic Cross-Coupling of Nitriles and Organobromides to Access Ketones
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Herein, we report the development of a dual catalytic approach for the cross-coupling of nitriles with aryl- and aliphatic-bromides. A titanium(III) catalyst is used to activate nitriles enabling their coupling with organobromides through a nickel catalyst. The Ni/Ti system efficiently prepared unsymmetrical ketones with good chemoselectivity and could selectively couple a bromide in the presence of other functionalizable handles.
- Chenniappan, Vinoth Kumar,Silwal, Sajan,Rahaim, Ronald J.
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p. 4539 - 4544
(2018/05/23)
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- Two-Step One-Pot Synthesis of Unsymmetrical (Hetero)Aryl 1,2-Diketones by Addition-Oxygenation of Potassium Aryltrifluoroborates to (Hetero)Arylacetonitriles
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An efficient one-pot two-step procedure for the synthesis of unsymmetrical (hetero)aryl 1,2-diketones has been developed. The reaction proceeds through a palladium-catalyzed nucleophilic addition of potassium aryltrifluoroborates to aliphatic nitriles followed by a copper-catalyzed aerobic benzylic C–H oxygenation using molecular oxygen as a green oxidant. This represents the first example of the direct synthesis of unsymmetrical diaryl 1,2-diketones from arylacetonitriles. This method utilizes inexpensive, stable, nontoxic, and readily available starting materials, is highly effective in the presence of both electron-rich and electron-poor nitriles and aryltrifluoroborates, and tolerates a wide variety of functional groups. The synthetic utility of this transformation was shown by increasing the scale of the reaction and by carrying out the one-pot protocol for the preparation of quinoxaline and benzimidazole derivatives. A plausible reaction mechanism has also been proposed.
- Kumar, Yogesh,Jaiswal, Yogesh,Kumar, Amit
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p. 494 - 505
(2018/02/09)
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- Metal-free synthesis of ketones by visible-light induced aerobic oxidative radical addition of aryl hydrazines to alkenes
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A green and cost-effective method has been developed for the conversion of alkenes to ketones under metal-free conditions. The reaction involves the oxidative addition of alkenes with aryl radicals, which are generated by visible-light induced aerobic oxidation of arylhydrazines. The key features of this reaction include broad substrate scope, readily available reagents and amenability to gram-scale synthesis.
- Ding, Ya,Zhang, Wenkai,Li, Hao,Meng, Yunge,Zhang, Te,Chen, Qiu-Yun,Zhu, Chunyin
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supporting information
p. 2941 - 2944
(2017/07/24)
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- Exploiting Aryl Mesylates and Tosylates in Catalytic Mono-α-arylation of Aryl- and Heteroarylketones
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The first general palladium catalyst for the catalytic mono-α-arylation of aryl- and heteroarylketones with aryl mesylates and tosylates is described. The newly developed indolyl-derived phosphine ligand L7 has been identified to promote this reaction eff
- Fu, Wai Chung,So, Chau Ming,Yuen, On Ying,Lee, Irene Toi Chuk,Kwong, Fuk Yee
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supporting information
p. 1872 - 1875
(2016/05/19)
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- Copper-catalyzed base-accelerated direct oxidation of C-H bond to synthesize benzils, isatins, and quinoxalines with molecular oxygen as terminal oxidant
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We describe herein an efficient and general copper (II)-catalyzed base-accelerated oxidation of the C-H bond to synthesize benzils and isatins. With similar oxidation system an efficient one-pot procedure for the synthesis of quinoxaline derivatives was realized. The two protocols feature using molecular oxygen as terminal oxidant, low catalyst loading, wide substrate scope, and high functional-group tolerance.
- Yu, Jing-Wen,Mao, Shuai,Wang, Yong-Qiang
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p. 1575 - 1580
(2015/03/14)
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- An expedient route to heterocycles through α-arylation of ketones and arylamides by microwave induced thermal SRN1 reactions
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Microwave irradiation promotes a quick aromatic nucleophilic substitution by a thermally induced electron transfer process to form new C-C bonds by the coupling of aryl radicals and enolate nucleophiles. Diverse 2-aryl-1- phenylethanones can be prepared by the direct α-arylation of acetophenone with different haloarenes. The ketone enolate anion is generated by deprotonation with tBuOK in DMSO and the reaction is carried out in a closed microwave vessel at 70-100°C for 10 min. This simple procedure also allows the synthesis of deoxybenzoin and indole heterocycle derivatives by inter- or intra-molecular ring closure reactions, with moderate to excellent substitution yields. This journal is the Partner Organisations 2014.
- Soria-Castro, Silvia M.,Caminos, Daniel A.,Penenory, Alicia B.
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p. 17490 - 17497
(2014/05/06)
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- Ruthenium-catalyzed cascade C-H functionalization of phenylacetophenones
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Three orthogonal cascade C-H functionalization processes are described, based on ruthenium-catalyzed C-H alkenylation. 1-Indanones, indeno indenes, and indeno furanones were accessed through cascade pathways by using arylacetophenones as substrates under conditions of catalytic [{Ru(p-cymene)Cl2}2] and stoichiometric Cu(OAc) 2. Each transformation uses C-H functionalization methods to form C-C bonds sequentially, with the indeno furanone synthesis featuring a C-O bond formation as the terminating step. This work demonstrates the power of ruthenium-catalyzed alkenylation as a platform reaction to develop more complex transformations, with multiple C-H functionalization steps taking place in a single operation to access novel carbocyclic structures. Carbon coupling cascade: Arylacetophenones react with Michael acceptors under ruthenium catalysis to set up triple and quadruple C-H functionalization pathways. Through choice of reaction conditions, novel indanone carbacycles, indeno indene carbacycles, and indeno furanone heterocycles can each be accessed in a single step.
- Mehta, Vaibhav P.,Garcia-Lopez, Jose-Antonio,Greaney, Michael F.
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supporting information
p. 1529 - 1533
(2014/03/21)
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- Palladium-catalyzed carbonylative negishi-type coupling of aryl iodides with benzyl chlorides
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Do the competition: The synthesis of 1,2-diarylethanones has been accomplished using the palladium-catalyzed coupling of aryl iodides and CO/benzyl chlorides or benzoyl chlorides. These reactions proceed smoothly in the presence of zinc powder to afford the products in moderate to excellent yields.
- Wu, Xiao-Feng,Schranck, Johannes,Neumann, Helfried,Beller, Matthias
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supporting information; experimental part
p. 40 - 44
(2012/03/11)
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- One-pot synthesis of useful heterocycles in medicinal chemistry using a cascade strategy
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To access useful heterocycles in medicinal chemistry such as pyridazinones, dihydropyrimidinones, and dihydropyrimidinthiones, a "green" mild and highly efficient one-pot triple cascade was developed involving a Claisen-decarboxylation, electrophilic reaction, and subsequent heterocyclization. In addition, indazoles and benzofurans could also be constructed via a double cascade. To develop the cascade process, a direct Claisen-decarboxylation reaction was firstly optimized. This reaction can then couple with electrophilic reactions including alkylation, Michael addition or aldol reaction to enable the preparation of various aryl ketones in a one-pot fashion. The Royal Society of Chemistry 2012.
- Wu, Guiyong,Yin, Weiyu,Shen, Hong C.,Huang, Yong
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supporting information; experimental part
p. 580 - 585
(2012/04/23)
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- Nickel-catalyzed intermolecular insertion of aryl iodides to nitriles: A novel method to synthesize arylketones
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A novel procedure for the NiCl2(DME)/dppp/Zn system catalyzed intermolecular insertion of aryl iodides to nitriles was developed, which afforded variously substituted arylketone derivatives in moderate to good yields with tolerance of a wide variety of functional groups.
- Hsieh, Jen-Chieh,Chen, Yen-Chung,Cheng, An-Yi,Tseng, Hsiao-Chun
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supporting information; experimental part
p. 1282 - 1285
(2012/04/23)
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- Palladium-catalyzed mono-α-arylation of carbonyl-containing compounds with aryl halides using dalphos ligands
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We report the extension and optimization of the [Pd(cinnamyl)Cl] 2/DalPhos catalyst system, previously found effective for the mono-α-arylation of acetone, to the mono-α-arylation of a variety of carbonyl-containing compounds with aryl halides and heteroaryl halides. Aryl methyl ketones, heteroaryl methyl ketones, propiophenones, malonates, and methoxyacetone can be α-arylated under relatively mild conditions and in good yields. We also report the limitations of the ligand/catalyst system towards other classes of carbonyl-containing compounds. We report the application of the [Pd(cinnamyl)Cl]2/DalPhos catalyst system, previously found effective for the mono-α-arylation of acetone, to the mono-α-arylation of a variety of carbonyl-containing compounds with aryl halides and heteroaryl halides.
- Crawford, Sarah M.,Alsabeh, Pamela G.,Stradiotto, Mark
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p. 6042 - 6050,9
(2020/09/02)
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- Aryl(chloro)methyl 4-tolyl sulfoxides: Synthesis and application to the synthesis of α-aryl ketones
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Aryl(chloro)methyl 4-tolyl sulfoxides were synthesized from arylmethyl 4-tolyl sulfoxides in moderate-to-good yields by sequential treatment with lithium diisopropylamide and tosyl chloride at low temperatures. Treatment of the lithium α-sulfinyl carbanion of the aryl(chloro)methyl 4-tolyl sulfoxides with aldehydes or ketones resulted in the formation of adducts in good-to-high yields. Treatment of these adducts with tert-butylmagnesium chloride gave the corresponding magnesium alkoxides. On treatment with isopropylmagnesium chloride, the alkoxides gave the corresponding magnesium β-oxido carbenoids, which rearranged to give α-aryl ketones in good-to-high yields. The magnesium enolate intermediates generated by rearrangement of the -oxido carbenoids could also be trapped with electrophiles to give α-aryl α-substituted ketones. These procedures offer a good method for the synthesis of a variety of α-aryl ketones from aldehydes and ketones. Georg Thieme Verlag Stuttgart. New York.
- Fukuda, Shigehiko,Tsuji, Kazuhito,Musashi, Jun,Nonaka, Ryo,Kimura, Tsutomu,Satoh, Tsuyoshi
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p. 3615 - 3626
(2011/12/16)
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- Arylation of α-pivaloxyl ketones with arylboronic reagents via Ni-catalyzed sp3 C-O activation
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A Suzuki-Miyaura coupling of α-pivaloxyl ketones via Ni-catalyzed sp3 C-O activation to produce α-aryl ketones is developed. This study offers a convenient method to construct α-arylation products from readily available α-hydroxyl carbonyl compounds.
- Huang, Kun,Li, Gang,Huang, Wei-Ping,Yu, Da-Gang,Shi, Zhang-Jie
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p. 7224 - 7226
(2011/08/09)
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- Palladium-catalyzed carbonylative suzuki coupling of benzyl halides with potassium aryltrifluoroborates in aqueous media
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A general palladium-catalyzed carbonylative cross-coupling reaction of benzyl chlorides with potassium aryltrifluoroborates in water has been developed. Applying this improved methodology 16 different 1,2-diarylethanones have been synthesized in 40-89% yield. Copyright
- Wu, Xiao-Feng,Neumann, Helfried,Beller, Matthias
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experimental part
p. 788 - 792
(2011/05/15)
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- Palladium-catalyzed α-ketone arylation under mild conditions
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The α-arylation of ketones with aryl halides catalyzed by the easily prepared and air-stable palladium complex (SIPr)Pd(Py)Cl2 (3) is described. Complex 3 displays high activity for a variety of aryl halides (activated, unactivated, and sterically hindered aryl halides) under mild conditions. Moreover, both aryl and alkyl ketones can be arylated. The α-arylation of some alkyl ketones can even be run at room temperature. The mono- or diarylated products of the unhindered dialkyl ketone 3-pentanone could be controlled by temperature and the ratio of ketones to aryl halides. Palladium-catalyzed α-ketone arylation of aryl and alkyl ketones with aryl halides is described. A total of 31 examples is presented with yields ranging from 45 to 95%.The mono- or diarylated product of the unhindered dialkyl ketone 3-pentanone could be controlled. Copyright
- Cao, Changsheng,Wang, Lingling,Cai, Zhengyuan,Zhang, Lingqiao,Guo, Jin,Pang, Guangsheng,Shi, Yanhui
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supporting information; experimental part
p. 1570 - 1574
(2011/04/17)
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- Palladium-catalyzed carbonylative coupling of benzyl chlorides with aryl boronic acids in aqueous media
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A novel chemoselective protocol for the carbonylative Suzuki coupling of benzyl chlorides with aryl boronic acids at low pressure of carbon monoxide has been developed. Applying a commercially available palladium acetate/PCy 3 catalyst system in the presence of potassium phosphate as the base and water as the solvent the coupling reactions proceeded smoothly. To demonstrate the general applicability 12 different α-arylated acetophenones have been synthesized in moderate to good yields (41-78%) under mild conditions.
- Wu, Xiao-Feng,Neumann, Helfried,Beller, Matthias
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experimental part
p. 6146 - 6149
(2010/12/24)
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- THERAPEUTIC FLUOROETHYL UREAS
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Compounds of the formula or a pharmaceutically acceptable salt thereof or a tautomer thereof, wherein A and B are as described herein, are useful for treating conditions afflicting mammals.
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Page/Page column 16
(2008/06/13)
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- The chemistry of α,β-ditosyloxyketones: Novel routes for the synthesis of desoxybenzoins and α-aryl-β-ketoaldehyde dimethylacetals from α,β-chalcone ditosylates
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The reaction of α,β-chalcone ditosylates 3 with potassium hydroxide in suitable conditions leads to 1,2-aryl shift and carbon-carbon bond cleavage, thereby providing a novel route for the synthesis of 1,2-diarylethan-1-ones 4 and 1,2-diaryl-3,3-dimethoxy propan-1-ones 5. Georg Thieme Verlag Stuttgart.
- Prakash, Om,Kumar, Rajesh,Sharma, Deepak,Pannu, Kamaljeet,Kamal, Raj
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p. 2189 - 2192
(2008/02/10)
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- Development of a practical synthesis of novel, pyrrole-based HMG-CoA reductase inhibitors
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This paper describes the development of an efficient and scalable second generation synthesis of novel, pyrrole-based HMG-CoA reductase inhibitors. Compound 1 was identified as part of a discovery program aimed at finding improved treatments for hypercholesterolemia. Herein, we describe an efficient synthesis of its highly functionalized pyrrole core followed by attachment of the 3,5-dihydroxyhexanoic acid side chain via ylide olefination chemistry.
- Pfefferkorn, Jeffrey A.,Bowles, Daniel M.,Kissel, William,Boyles, David C.,Choi, Chulho,Larsen, Scott D.,Song, Yuntao,Sun, Kuai-Lin,Miller, Steven R.,Trivedi, Bharat K.
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p. 8124 - 8134
(2008/02/08)
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- PCP-Bis(phosphinite) pincer complexes: new homogeneous catalysts for α-arylation of ketones
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Two new p-alkoxycarbonylated palladium bis(phosphinite) PCP pincer complexes are easily prepared and for the first time evaluated as homogeneous catalysts in α-arylation of ketone enolates. Apart from the total absence of phenyl-aryl exchange by-products and significantly low catalyst loadings, the general α-arylation protocols described in this letter feature not only a broad applicability to a range of ketones and aryl bromides with marked electronic and steric differences but also the possibility to generate mono-diarylated products.
- Churruca, Fátima,SanMartin, Raul,Tellitu, Imanol,Domínguez, Esther
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p. 3233 - 3237
(2007/10/03)
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- N-ALKYL PYRROLES AS HMG-COA REDUCTASE INHIBITORS
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HMGCo-A reductase inhibitor compounds useful as hypocholesterolemic and hypolipidemic compounds are provided. Also provided are pharmaceutical compositions of the compounds. Methods of making and methods of using the compounds are also provided. Formula (I).
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Page/Page column 142
(2010/02/12)
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- Towards a facile synthesis of triarylethanones: Palladium-catalyzed arylation of ketone enolates under homogeneous and heterogeneous conditions
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The palladium-catalyzed regioselective α-monoarylation of deoxybenzoins and α,α-diarylation of acetophenones provides general, efficient access to 1,2,2-triarylethanones. After a comprehensive search for suitable experimental conditions to optimize such transformations, both reactions are alternatively conducted by means of either commercially available polymer-anchored catalysts or a very simple homogeneous catalytic system, thus avoiding the use of complex ligands. In addition, the synthesis of deoxybenzoins employing polymer-supported fibrous palladium catalysts is reported for the first time, and the excellent catalyst recycling properties suggest applicability to industrial purposes.
- Churruca, Fátima,SanMartin, Raul,Carril, Mónica,Tellitu, Imanol,Domínguez, Esther
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p. 2393 - 2408
(2007/10/03)
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- Direct preparation of benzylic manganese reagents from benzyl halides, sulfonates, and phosphates and their reactions: Applications in organic synthesis
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The use of highly active manganese (Mn)*, prepared by the Rieke method, was investigated for the direct preparation of benzylic manganese reagents. The oxidative addition of the highly active manganese to benzylic halides was easily completed under mild conditions. Moreover, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. Most of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. In addition, the use of highly active manganese was also studied for preparation of homo-coupled products of functionalized benzyl halides without transition metal catalysts. These useful approaches provided not only a facile synthetic route to the preparation of resoricinolic lipids but a facile synthesis of functionalized 4-benzylpyridines by regioselective and chemo selective γ-addition of benzylic group to N-alkoxycarbonylpyridinum salts.
- Suh, YoungSung,Lee, Jun-Sik,Kim, Seoung-Hoi,Rieke, Reuben D.
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- Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in Organic Synthesis
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The use of highly active manganese, prepared by the Rieke method, for the direct preparation of benzylic manganese reagents was investigated. The oxidative addition of the highly active manganese (Mn*) to benzylic halides was easily completed under mild conditions. More importantly, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. The majority of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. This approach also provided a facile synthetic route to the preparation of resorcinolic lipids.
- Kim, Seung-Hoi,Rieke, Reuben D.
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p. 2322 - 2330
(2007/10/03)
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- Nickel-catalyzed direct electrochemical cross-coupling between aryl halides and activated alkyl halides
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The electrochemical reduction of a mixture of aryl halides and activated alkyl halides in DMF in the presence of catalytic amount of NiBr2bipy leads to cross-coupling products in good to high yields. The method applies to the synthesis of α-aryl ketones, α-aryl esters, and allylated compounds from readily available organic halides. Optimization of the process has been obtained by slowly adding the most reactive organic halide (usually the activated alkyl halide) during the electrolysis which is best conducted at 70 °C when aryl bromides are involved.
- Durandetti, Muriel,Nedelec, Jean-Yves,Perichon, Jacques
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p. 1748 - 1755
(2007/10/03)
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- A novel method of arylation of α-chloroketones
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α-Arylated ketones were obtained in moderate to good yields by one-step electroreductive coupling of α-chloroketones and arylhalides in DMF and in the presence of a Al- or Zn-sacrificial anode and a catalytic amount of a nickel complex.
- Durandetti,Sibille,Nedelec,Perichon
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p. 145 - 151
(2007/10/02)
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- 10,5-(Iminomethano)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene and derivatives. Potent PCP receptor ligands
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IDDC (3, 10,5-(iminomethano)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene) and a series of substituted derivatives were synthesized and evaluated in vitro for their ability to displace tritiated MK-801 ([3H]-2) from its specific binding site in guinea pig brain homogenate. Substitution at the 3- position of 3 with bromine, chlorine, and fluorine led to increased binding affinity. In contrast, substitution of donor groups at the 3-position gave decreased binding affinities, as did all substitutions at the 7-position and on nitrogen. Where racemic mixtures were resolved, the (+)-optical antipodes were more active than their enantiomers or racemates. The most active ligand found in this study was (+)-13e (IC50 = 15.5 ± 4.5 nM). The affinity of (+)-13e for the PCP receptor makes it among the most potent ligands known. In vitro neuroprotection was demonstrated by 3, (+)-3, and (+)-6 (N-Me-IDDC) against glutamate-induced cell death in rat hippocampal cells.
- Gee,Barmettler,Rhodes,McBurney,Reddy,Hu -,Cotter,Hamilton,Weber,Keana
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p. 1938 - 1946
(2007/10/02)
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- PHOSPHORUS-CONTAINING HMG-COA REDUCTASE INHIBITORS, NEW INTERMEDIATES AND METHOD
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Compounds which are useful as inhibitors of cholesterol biosynthesis and thus as hypocholesteroleumic agents are provided which have the structure STR1 wherein R is OH, or salts thereof or lower alkoxy; R. sup.x is H or alkyl;X is--CH 2--,--
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- Cholesterol biosynthesis inhibiting pyrazole analogs of mevalonolactone and its derivatives
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Compounds of the formula STR1 wherein R1 is C1-6 alkyl not containing an asymmetric carbon atom, each of R2 and R5 is independently hydrogen, C1-3 alkyl, n-butyl, i-butyl, t-butyl, C1-3 alk
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- Metallic Nickel-Mediated Synthesis of Ketones by the Reaction of Benzylic, Allylic, Vinylic, and Pentafluorophenyl Halides with Acid Halides
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Metallic nickel was investigated as a convenient coupling reagent for the synthesis of ketones by the reaction of benzylic, allylic, vinylic, and pentafluorophenyl halides with acid halides at 85 deg C in glyme.A variety of benzylic ketones with functional groups including halogen, cyano, methoxycarbonyl, and hydroxycarbonyl groups were prepared in good yields by this method.The reaction was demonstrated to proceed via organonickel halide intermediates formed by the smooth oxidative addition of benzylic and acyl halides to metallic nickel, which were trapped with electron-deficient olefins. (?-Allyl)nickel halides, prepared in situ at 85 deg C from allylic halides and the nickel, also worked for the preparation of ketones.Vinylic and pentafluorophenyl halides but not alkyl halides reacted with acid halides to give the corresponding ketones in moderate yields.
- Inaba, Shin-ichi,Rieke, Reuben D.
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p. 1373 - 1381
(2007/10/02)
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- STRUCTURES IN SOLUTION OF ADDUCTS OF 2,8-DIOXA-5-AZA-1-PHOSPHABICYCLOOCTANE AND SUBSTITUTED BENZILS
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Adducts of 2,8-dioxa-5-aza-1-phosphabicyclooctane and p,p'-dimethylbenzil, p-methoxy-p'-fluorobenzil, p-fluorobenzil, p,p'-difluorobenzil, p-nitrobenzil and p,p'-dinitrobenzil have been prepared.Although these materials could not be isolated in pure form because of rapid decomposition, the 31P and other NMR spectral data indicate that all of these materials are pentacoordinate in solution.The NMR data also indicate that all of these adducts undergo rapid intramolecular ligand reorganosation at room temperature.Variable temperature NMR measurements indicate that these rearrangements can be slowed and that they all have virtually the same activation energies, ΔG(excit.) 11.4-11.9 kcal/mole.The barrier to ligand reorganization is associated with the 5-membered dioxa containing ring adopting a diequatorial disposition.These results are discussed and compared to other systems.
- Denney, Donald B.,Denney, Dorothy Z.,Pastor, Stephen D.
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p. 191 - 198
(2007/10/02)
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