- An efficient palladium-catalyzed coupling reaction of lithium alkynyltriisopropoxyborates with acid chlorides: A new access to synthesis of conjugated ynones
-
An efficient palladium-catalyzed protocol for the synthesis of ynones from lithium alkynyltriisopropoxyborates with acid chlorides under mild neutral conditions.
- Oh, Chang Ho,Reddy, V. Raghava
-
-
Read Online
- Ni(0) catalyzed one step synthesis of benzo[b][1,8] naphthyridin-5-ones from silyl-α-ketoalkynes in water
-
One-step synthesis of new benzo[b][1,8]naphthyridin-5-ones using a Ni(0) catalytic system in aqueous medium with mild conditions of pressure and temperature is described. It is very interesting to note that Ni(0) catalyst increases the rate of condensation of several α-ketoalkynes with 2-amino-4(1H)-quinolinone obtaining benzo[b][1,8]naphthyridin-5-ones in very high yield. In the absence of catalyst this condensation reaction takes 24 h with a product yield of 10%.
- Suárez-Ortiz, Gloria Alejandra,Sharma, Pankaj,Amézquita-Valencia, Manuel,Arellano, Ivonne,Cabrera,Rosas, Noé
-
-
Read Online
- Palladium-Catalyzed Reactions of Acyl Chlorides with (1-Alkynyl)tributylstannanes. A Convenient Synthesis for 1-Alkynyl Ketones
-
Acyl chlorides couple with (1-alkynyl)tributylstannanes in the presence of catalytic amounts of palladium(II) or palladium(0) complexes to produce 1-alkynyl ketones in respectable yields.The couplings of isobutyryl, acetyl, benzoyl, and p-nitrobenzoyl chlorides with phenylethynyl-, (trimethylsilyl)ethynyl-, (carbomethoxy)ethynyl-, -1-propynyl>-, and (3,3-diethoxy-1-propynyl)tributylstannanes were investigated in the presence of tetrakis(triphenylphosphine)palladium(O), benzylchlorobis(triphenylphosphine)palladium(II), dichlorobis(triphenylphosphine)palladium(II), or phenyliodobis(triphenylphosphine)palladium(II).The reactions are highly selective in that only the alkynyl groups are transferred from the stannane.
- Logue, Marshall W.,Teng, Kelly
-
-
Read Online
- MeOTf-Mediated Alkynylation of Selenoamides Leading to β-Methylselenenyl α,β-Unsaturated Ketones and Their Characterization
-
(formula presented) β-Methylselenenyl α,β-unsaturated ketones were effectively synthesized by treating selenoamides with methyl triflate, followed by reaction with lithium acetylides. The reaction proceeded with high stereoselectivity to give exclusively Z-isomers. 77Se NMR studies and X-ray molecular structure analysis of β-methyselenenyl α,β-unsaturated ketones suggested that the products show 1,5-nonbonding interaction between the selenium atom and carbonyl oxygen atom.
- Murai, Toshiaki,Mutoh, Yuichiro,Kato, Shinzi
-
-
Read Online
- Straightforward Novel One-Pot Enaminone and Pyrimidine Syntheses by Coupling-Addition-Cyclocondensation Sequences
-
The coupling of acid chlorides 1 with terminal alkynes 2 using only one equivalent (!) of triethylamine under Sonogashira conditions followed by subsequent addition of primary or secondary amines 4 to the intermediate alkynones 3 represents a straight-for
- Karpov, Alexei S.,Mueller, Thomas J. J.
-
-
Read Online
- C-C-bond formation in reactions of [(η5-C5H4SiMe3)2Ti(C?CR1)2]CuR with acyl chlorides and anhydrides
-
The chemical behaviour of selected {[Ti](C?CR1)2}CuR complexes (1a: R1=SiMe3, R=CH3; 1b: R1=tBu, R=CH3; 1c: R1=tBu, R=C?CSiMe3) towards a number of different acyl chlorides and anhydrides is described. The reaction of 1a or 1b with R2C(O)Cl (2a: R2=CH3, 2b: R2=C6H5) produces the ketones R2C(O)R (4a: R=R2=CH3; 4b: R=CH3, R2=C6H5; 4c: R=C?CSiMe3, R2=CH3, 4d: R=C?CSiMe3, R2=C6H5) along with {[Ti](Cnequiv;CR1)2}CuCl (3a: R1=SiMe3, 3b: R1=tBu). However, on treatment of 1b or 1c with [CH3C(O)]2O (5a) the ketones 4a or 4c are formed along with the copper(I) acetate complex {[Ti](C?CtBu)2}CuOC(O)CH3 (6), while the reaction of 1b or 1c with CH3CO2H (5b) yields methane and 6. In addition, when 1b or 1c are reacted with maleic (7), phthalic (9a) or tetrachlorophthalic anhydride (9b) the copper(I) carboxylates {[Ti](C?CtBu)2}CuOC(O)-cis-CH=CH-C(O)R (8a: R=CH3, 8b: R=C?CSiMe3) and {[Ti](C?CtBu)2}CuOC(O)-C6H4-n Cln-2-C(O)R (10a: n=0, R=CH3; 10b: n=0, R=C?CSiMe3; 10c: n=4, R=C?CSiMe3) are produced, which upon addition of, e.g. HBr afford via cleavage of the copper-oxygen σ-bond {[Ti](C?CtBu)2}CuBr (3c) and the corresponding carboxylic acids cis-HO2C-CH=CH-C(O)CH3 (11a) or HO2C-C6H4-2-C(O)CH3 (11b), respectively.
- Frosch,Back,Lang
-
-
Read Online
- Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol with oxygen as oxidizing agent and application
-
The invention discloses a copper-catalyzed method for preparing an aldehyde or ketone compound by oxidizing alcohol with oxygen as an oxidizing agent. Reaction is performed in an organic solvent for 4-48 hours at room temperature by using copper salt and nitroxide free radicals as catalysts and oxygen or air as an oxidizing agent to efficiently oxidize an alcohol compound into the corresponding aldehyde or ketone compound. The method is simple to operate, free of chlorides corrosive to equipment, available in raw materials and reagents, mild in reaction conditions, wide in substrate universality, good in functional group compatibility, convenient in separation and purification, environmentally friendly in the whole process and free of pollution, and is a method suitable for industrial production.
- -
-
Paragraph 0028-0030; 0064-0069
(2020/08/18)
-
- Copper-Catalyzed Aminoboration from Hydrazones to Generate Borylated Pyrazoles
-
Herein we report an aminoboration reaction that employs inexpensive, Earth-abundant, and commercially available Cu(OTf)2 as an effective catalyst in the direct addition of B-N σ bonds to C-C π bonds, generating borylated pyrazoles, which are us
- Tu, Kim N.,Kim, Scott,Blum, Suzanne A.
-
supporting information
p. 1283 - 1286
(2019/02/26)
-
- Metal-Free Promoted CF2/CF3-Difunctionalization of Unactivated Alkenes
-
An operationally simple radical difluoroalkylation/trifluoromethylation and alkynylation of unactivated alkenes under mild conditions has been developed. Through this protocol, a series of CF2/CF3- substituted linear alkynyl ketones
- Li, Ming,Zhu, Xin-Yu,Qiu, Yi-Feng,Han, Ya-Ping,Xia, Yu,Wang, Cui-Tian,Li, Xue-Song,Wei, Wan-Xu,Liang, Yong-Min
-
supporting information
p. 2945 - 2950
(2019/04/27)
-
- Visible-light-mediated dehydrogenative cross-coupling between terminal alkynes and aldehydes by employing a supramolecular polymeric ensemble of PBI derivative
-
A supramolecular polymer of PBI derivative and ZnO NPs has been developed which exhibits remarkable efficiency in direct dehydrogenative cross-coupling between terminal alkynes and aldehydes for the synthesis of ynones under photocatalytic conditions.
- Kataria, Meenal,Deol, Harnimarta,Singh, Gurpreet,Kumar, Manoj,Bhalla, Vandana
-
supporting information
p. 822 - 826
(2018/02/06)
-
- 1,1-Diphosphines and divinylphosphines via base catalyzed hydrophosphination
-
A catalytic hydrophosphination route to 1,1-diphosphines is yet to be reported: these narrow bite angle pro-ligands have been used to great effect as ligands in homogeneous catalysis. We herein demonstrate that terminal alkynes readily undergo double hydrophosphination with HPPh2 and catalytic potassium hexamethyldisilazane (KHMDS) to generate 1,1-diphosphines. A change to H2PPh leads to the formation of P,P-divinyl phosphines.
- Coles,Mahon,Webster
-
supporting information
p. 10443 - 10446
(2018/09/21)
-
- Cascade and Effective Syntheses of Functionalized Tellurophenes
-
A one-pot and transition-metal-catalyst-free synthetic strategy to construct functionalized tellurophenes has been developed. Substituted 1,1-dibromo-1-en-3-ynes are smoothly converted to tellurophenes with telluride salts in high yield via a series of cascade reactions through reductive debromination, hydrotelluration, nucleophilic cyclization, and aromatization. Close inspection of the results clearly showed that the reactivity of in situ prepared telluride salts are significantly influenced by the polarity of the solvent system and the electronic nature of the substituent on the enyne substrate. This method reports the first direct synthesis of 3-aryltellurophenes in high yields at room temperature. This novel reaction strategy is also found to be a promising synthetic method for multisubstituted tellurophenes and selenophenes.
- Karapala, Vamsi Krishna,Shih, Hong-Pin,Han, Chien-Chung
-
p. 1550 - 1554
(2018/03/23)
-
- A phosphine-free, atom-efficient cross-coupling reaction of triorganoindiums with acyl chlorides catalyzed by immobilization of palladium(0) in MCM-41
-
The first phosphine-free heterogeneous palladium(0)-catalyzed cross-coupling of triorganoindiums with acyl chlorides has been developed that proceeds smoothly in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable aryl ketones and α,β-acetylenic ketones with high atom-economy and high yield. This phosphine-free heterogeneous palladium(0) catalyst can be easily prepared from commercially available reagents and recovered by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
- Miao, Jiankang,Huang, Bin,Liu, Haiyi,Cai, Mingzhong
-
p. 42570 - 42578
(2017/09/11)
-
- Oxyboration with and without a Catalyst: Borylated Isoxazoles via B-O-Bond Addition
-
Herein we report an oxyboration reaction with activated substrates that employs B-O σ bond additions to C-C π bonds to form borylated isoxazoles, which are potential building blocks for drug discovery. Although this reaction can be effectively catalyzed by gold, it is the first example of uncatalyzed oxyboration of C-C π bonds by B-O σ bonds-and only the second example that is catalyzed. This oxyboration reaction is tolerant of groups incompatible with alternative lithiation/borylation and palladium-catalyzed C-H activation/borylation technologies for the synthesis of borylated isoxazoles.
- Tu, Kim N.,Hirner, Joshua J.,Blum, Suzanne A.
-
supporting information
p. 480 - 483
(2016/02/18)
-
- Consecutive three- and four-component coupling-Bagley-Bohlmann-Rahtz syntheses of tri- and tetrasubstituted pyridines
-
The concatenation of the modified Sonogashira alkynone synthesis and the Bagley-Bohlmann-Rahtz pyridine synthesis gives novel consecutive three- and four-component coupling-Bagley-Bohlmann-Rahtz (cBBR) syntheses of tri- and tetrasubstituted pyridines in a one-pot fashion. With these processes 15 differently substituted 3-ethoxycarbonyl 2-methylpyridines can be readily obtained in modest to moderate yields.
- Dohe, Janis,Müller, Thomas J. J.
-
p. 705 - 718
(2016/07/06)
-
- Zinc-Catalyzed Dehydrogenative Cross-Coupling of Terminal Alkynes with Aldehydes: Access to Ynones
-
Because of the lack of redox ability, zinc has seldom been used as a catalyst in dehydrogenative cross-coupling reactions. Herein, a novel zinc-catalyzed dehydrogenative C(sp2)-H/C(sp)-H cross-coupling of terminal alkynes with aldehydes was dev
- Tang, Shan,Zeng, Li,Liu, Yichang,Lei, Aiwen
-
supporting information
p. 15850 - 15853
(2016/01/29)
-
- Oxidative Coupling of Terminal Alkynes with Aldehydes Leading to Alkynyl Ketones by Using Indium(III) Bromide
-
An indium(III)-promoted direct acylation of terminal alkynes using aldehydes leading to ynones was developed. In contrast to the previous addition reactions of alkynes to aldehydes, which provide propargylic alcohols, the oxidative coupling proceeded exclusively to afford alkynyl ketones. The products were likely generated through an Oppenauer oxidation of the indium propargylic alkoxide species by excess amounts of aldehydes.
- Ogiwara, Yohei,Kubota, Masahito,Kurogi, Kotaro,Konakahara, Takeo,Sakai, Norio
-
supporting information
p. 18598 - 18600
(2016/01/25)
-
- Synthesis of 3-carbonyl pyrazole-5-phosphonates via 1,3-dipolar cycloaddition of Bestmann-Ohira reagent with ynones
-
The present work explores the hitherto unexplored reactivity of ynones as dipolarophiles with Bestmann-Ohira reagent. The reaction offers a convenient route for the synthesis of regioisomerically pure 3,5-disubstituted or 3,4,5-trisubstituted pyrazoles in
- Pramanik, Mukund M.D.,Kant, Ruchir,Rastogi, Namrata
-
p. 5214 - 5220
(2014/07/08)
-
- Synthesis of 3-carbonyl pyrazole-5-phosphonates via 1,3-dipolar cycloaddition of Bestmann-Ohira reagent with ynones
-
The present work explores the hitherto unexplored reactivity of ynones as dipolarophiles with Bestmann-Ohira reagent. The reaction offers a convenient route for the synthesis of regioisomerically pure 3,5-disubstituted or 3,4,5-trisubstituted pyrazoles in
- Pramanik, Mukund M.D.,Kant, Ruchir,Rastogi, Namrata
-
p. 5214 - 5220
(2014/12/10)
-
- Condensation reactions of guanidines with bis-electrophiles: Formation of highly nitrogenous heterocycles
-
2-Amino-1,4-dihydropyrimidines were reacted with bis-electrophiles to produce novel fused bipyrimidine, pyrimidoaminotriazine, and pyrimidosulfonamide scaffolds. In addition, a quinazoline library was constructed using a guanidine Atwal-Biginelli reaction with 1-(quinazolin-2-yl)guanidines. The product heterocycles have novel constitutions with high nitrogen atom counts and represent valuable additions to screening libraries for the discovery of new modulators of biological targets.
- Arnold, David M.,Laporte, Matthew G.,Anderson, Shelby M.,Wipf, Peter
-
p. 7719 - 7731
(2013/08/23)
-
- Addition of terminal alkynes to aromatic nitriles catalyzed by divalent lanthanide amides supported by amidates: Synthesis of ynones
-
An efficient protocol has been established for the synthesis of conjugated ynones via addition of terminal alkynes to aromatic nitriles, which is catalyzed by novel divalent lanthanide amide complexes. All the reactions gave the products in good to excell
- Ding, Hao,Lu, Chengrong,Hu, Xiaolin,Zhao, Bei,Wu, Bing,Yao, Yingming
-
supporting information
p. 1269 - 1274
(2013/07/11)
-
- Base-mediated selective synthesis of diversely substituted N-heterocyclic enamines and enaminones by the hydroamination of alkynes
-
Regio- and stereoselective alkynylation of various N-heterocycles 1a-l using potassium and cesium salts in DMSO is described. Terminal alkynes 2a-k and internal alkynes 4a-f provided the kinetically stable Z-enamines 3a-l and 5a-i in good to excellent yields using KOH at 120 °C. Addition of heterocyclic amines to 1,3- and 1,4-diethynylbenzene 6a-b provided the mixture of E/Z isomers with KOH; however, with Cs2CO3 selectively Z-isomers 7ab-db were obtained by the hydroamination at one triple bond. This developed methodology also provides an easy and novel access for the synthesis of enaminones 10a-c. The detailed work also supports the formation of cis-isomer by preferential addition of o-haloarylalkynes followed by intramolecular C2 arylation in the copper-catalyzed tandem synthesis of indolo and pyrrolo[2,1-a]isoquinolines.
- Joshi, Megha,Patel, Monika,Tiwari, Rakesh,Verma, Akhilesh K.
-
experimental part
p. 5633 - 5645
(2012/08/07)
-
- Rhodium-catalyzed intra- and intermolecular [5 + 2] cycloaddition of 3-acyloxy-1,4-enyne and alkyne with concomitant 1,2-acyloxy migration
-
A new type of rhodium-catalyzed [5 + 2] cycloaddition was developed for the synthesis of seven-membered rings with diverse functionalities. The ring formation was accompanied by a 1,2-acyloxy migration event. The five- and two-carbon components of the cycloaddition are 3-acyloxy-1,4-enynes (ACEs) and alkynes, respectively. Cationic rhodium(I) catalysts worked most efficiently for the intramolecular cycloaddition, while only neutral rhodium(I) complexes could facilitate the intermolecular reaction. In both cases, electron-poor phosphite or phosphine ligands often improved the efficiency of the cycloadditions. The scope of ACEs and alkynes was investigated in both the intra- and intermolecular reactions. The resulting seven-membered-ring products have three double bonds that could be selectively functionalized.
- Shu, Xing-Zhong,Li, Xiaoxun,Shu, Dongxu,Huang, Suyu,Schienebeck, Casi M.,Zhou, Xin,Robichaux, Patrick J.,Tang, Weiping
-
p. 5211 - 5221
(2012/05/05)
-
- PROCESS FOR PRODUCING ALDEHYDES OR KETONES BY OXIDIZING ALCOHOLS WITH OXYGEN
-
Provided is a process for producing aldehydes or ketones by oxidizing alcohols with oxygen, which comprises oxidizing alcohols to aldehydes or ketones in an organic solvent at room temperature with oxygen or air as an oxidant, wherein ferric nitrate (Fe(NO3)3.9H2O), 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) and an inorganic chloride are used as catalysts, the reaction time is 1-24 hours, and the molar ratio of said alcohols, 2,2,6,6-tetramethylpiperidine N-oxyl and the inorganic chloride is 100:1?10:1?10:1?10. The present process has the advantages of high yield, mild reaction conditions, simple operation, convenient separation and purification, recoverable solvents, substrates used therefor being various and no pollution, and therefore it is adaptable to industrialization.
- -
-
Page/Page column 5
(2012/09/10)
-
- Synthesis of ynones via recyclable polystyrene-supported palladium(0) complex catalyzed acylation of terminal alkynes with acyl chlorides under copper- and solvent-free conditions
-
Herein, a highly efficient method for the copper- and solvent-free coupling reaction of acyl chlorides and terminal alkynes catalyzed by 1-phenyl-1,2-propanedione-2-oxime thiosemicarbazone-functionalized polystyrene resin-supported Pd(0) complex is descri
- Bakherad, Mohammad,Keivanloo, Ali,Bahramian, Bahram,Jajarmi, Saeideh
-
experimental part
p. 311 - 314
(2011/04/12)
-
- Rapid access to unusual solid-state luminescent merocyanines by a novel one-pot three-component synthesis
-
A novel consecutive three-component coupling-enamine addition synthesis gives access to three types of diene merocyanines in a selective fashion and in good yields. Moreover, all these push-pull systems are intensely red or yellow emissive in the solid st
- Muschelknautz, Christian,Frank, Walter,Mueller, Thomas J. J.
-
supporting information; experimental part
p. 2556 - 2559
(2011/06/23)
-
- One-pot three-step synthesis of 1,2,3-triazoles by copper-catalyzed cycloaddition of azides with alkynes formed by a Sonogashira cross-coupling and desilylation
-
A microwave-assisted, one-pot, three-step Sonogashira cross-coupling- desilylation-cycloaddition sequence was developed for the convenient preparation of 1,4-disubstituted 1,2,3-triazoles starting from a range of halides, acyl chlorides, ethynyltrimethyls
- Friscourt, Frederic,Boons, Geert-Jan
-
supporting information; experimental part
p. 4936 - 4939
(2010/12/25)
-
- An unexpected equilibrium process associated with a standard approach to ynone synthesis
-
A direct comparison between Weinreb amides and morpholine amides was made with regard to their reactions with alkynyllithium reagents to form ynones. While treatment with stoichiometric alkynyllithium generally effects complete reaction in the case of Weinreb amides, incomplete reactions are obtained from the corresponding morpholine amides. This difference is attributed to an unexpected equilibrium process in the latter case, and it is shown that the use of excess alkynyllithium reagent with morpholine amides provides a synthetically useful synthesis of ynones at 0 °C.
- Jackson, Mary M.,Leverett, Carolyn,Toczko, Jennifer F.,Roberts, John C.
-
p. 5032 - 5035
(2007/10/03)
-
- Carbon-carbon bond forming reactions by using bistrifluoromethanesulfonimide
-
Bistrifluoromethanesulfonimide has been used to catalyze C-C bond forming reactions such as Friedel-Crafts, Mukaiyama, 1,2-addition and 1,4-addition as well as C-glycosidation reactions.
- Cossy,Lutz,Alauze,Meyer
-
-
- Palladium-catalyzed cross-coupling reactions between 1-alkynylstibines and acyl chlorides
-
1-Alkynyldiphenylstibines react with acyl chlorides in dichloroethane in the presence of a palladium(0) or (II) catalyst to afford alkynyl ketones by cross-coupling reaction in good to moderate yields. These reactions are highly substituent-selective in that only the alkynyl group could be transferred from the antimony compounds, even in the presence of a large excess of acyl chlorides. (C) 2000 Elsevier Science Ltd.
- Kakusawa, Naoki,Yamaguchi, Kouichiro,Kurita, Jyoji,Tsuchiya, Takashi
-
p. 4143 - 4146
(2007/10/03)
-
- Synthesis and reactivity of 2,4,4-trimethyl-2-silylethynyl substituted 1,3-dioxanes
-
A synthesis was developed for 2,4,4-trimethyl-2-ethynyl substituted 1,3-dioxane. Hydrolysis and cleavage thereof at the Si-Csp bond was investigated.
- Kosulina,Ol'khovskaya,Kul'nevich
-
p. 608 - 613
(2007/10/03)
-
- A convenient synthesis of masked β-ketoaldehydes by the controlled addition of nucleophiles to (trimethylsilyl)ethynyl ketones
-
The controlled addition of nucleophiles to (trimethylsilyl)ethynyl ketones provides a facile route to β-ketoacetals, β-alkoxy-α,β-unsaturated ketones or vinylogous amides depending on the choice of reaction conditions.
- Bromidge,Entwistle,Goldstein,Orlek
-
p. 487 - 494
(2007/10/02)
-
- REACTION OF ALKYNYLTRIMETHYLSILANES WITH A HYPERVALENT ORGANOIODINE COMPOUND: A NEW GENERAL SYNTHESIS OF ALKYNYLIODONIUM SALTS
-
New general methods for the synthesis of alkynyl(phenyl)iodonium tetrafluoroborate 2 from alkynyltrimethylsilanes 1 utilizing the combination of iodosylbenzene and triethyloxonium tetrafluoroborate or boron trifluoride etherate were developed.The medium e
- Ochiai, Masahito,Kunishima, Munetaka,Sumi, Kenzo,Nagao, Yoshimitsu,Fujita, Eiichi,et al.
-
p. 4501 - 4504
(2007/10/02)
-