- Construction of a Pyrimidine Framework through [3 + 2 + 1] Annulation of Amidines, Ketones, and N, N-Dimethylaminoethanol as One Carbon Donor
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An efficient, facile, and eco-friendly synthesis of pyrimidine derivatives has been developed. It involves a [3 + 2 + 1] three-component annulation of amidines, ketones, and one carbon source. N,N-Dimethylaminoethanol is oxidized through C(sp3)-H activation to provide the carbon donor. One C-C and two C-N bonds are formed during the oxidative annulation process. The reaction shows good tolerance to many important functional groups in air, making this methodology a highly versatile alternative, and significant improvement to the existing methods for structuring a pyrimidine framework, especially 4-aliphatic pyrimidines.
- Qin, Zemin,Ma, Yongmin,Li, Fanzhu
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supporting information
p. 13734 - 13743
(2021/10/12)
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- I2-Catalyzed Aerobic α,β-Dehydrogenation and Deamination of Tertiary Alkylamines: Highly Selective Synthesis of Polysubstituted Pyrimidines via Hidden Acyclic Enamines
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A novel and efficient entrance to the pyrimidine skeleton has been presented via the α,β-dehydrogenation and deamination of tertiary alkylamines. This I2-catalyzed dehydrogenative multicomponent procedure utilizes simple aldehydes to trap the hidden enami
- Gao, Qinghe,Wu, Manman,Zhang, Ke,Yang, Ning,Liu, Mengting,Li, Juan,Fang, Lizhen,Bai, Suping,Xu, Yongtao
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supporting information
p. 5645 - 5649
(2020/07/24)
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- Synthesis method of pyrimidine compound containing alkyl and aryl
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The invention discloses a synthesis method of a pyrimidine compound containing alkyl and aryl, and belongs to the technical field of organic synthesis. Key points of the technical scheme of the invention are as follows: the synthesis method of the pyrimidine compound containing alkyl and aryl comprises the following specific steps: dissolving an aldehyde compound, an amidine hydrochloride compoundand a tertiary aliphatic amine compound in a solvent, adding an iodine reagent and an oxidant, and carrying out a reaction process at 110-150 DEG C to prepare the pyrimidine compound containing alkyland aryl as a target product. The synthesis process is simple and efficient, the pyrimidine compound is directly prepared by one step through a one-pot cascade reaction without transition metal catalysis so that resource waste and environmental pollution caused by use of various reagents in multi-step reaction, purification treatment of reaction intermediates in each step and the like are avoided, the synthesis process is convenient to operate, the raw materials are simple, the reaction conditions are mild, the substrate application range is wide, and meanwhile, alkyl substituents are ingeniously introduced by taking the tertiary fatty amine compound as the raw material.
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Paragraph 0013-0041
(2020/07/15)
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- Selective synthesis of pyrimidines from cinnamyl alcohols and amidines using the heterogeneous OMS-2 catalyst
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Herein, an efficient aerobic oxidative synthesis of pyrimidines was carried out using cinnamyl alcohols and amidines catalyzed by manganese oxide octahedral molecular sieve (OMS-2). The heterogeneous catalytic method features base-/additive-free conditions, wide substrate scope, use of O2 as a green oxidant, and simple operation. Moreover, the OMS-2 catalyst prepared by the conventional reflux method demonstrates catalytic selectivity, activity, and excellent recyclability.
- Shen, Jian,Meng, Xu
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- Heterogeneous gold(I)-catalyzed cyclization between ynals and amidines: An efficient and practical synthesis of 2,4-disubstituted pyrimidines
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A novel and highly efficient heterogeneous gold(I)-catalyzed cyclization between ynals and amidines has been developed that proceeds smoothly under mild conditions and provides a general and practical method for the synthesis of a wide variety of 2,4-disu
- Jiang, Minhua,Nie, Quan,Cai, Mingzhong
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p. 2488 - 2500
(2019/07/12)
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- Cross-Dehydrogenative Coupling of Heterocyclic Scaffolds with Unfunctionalized Aroyl Surrogates by Palladium(II) Catalyzed C(sp2)-H Aroylation through Organocatalytic Dioxygen Activation
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Cross-dehydrogenative coupling of biorelevant heterocyclic scaffolds with arylmethanes for aroylation during Pd(II)-catalyzed C(sp2)-H activation has been achieved through dioxygen activation by NHPI. Mass spectrometry and 1H NMR based kinetic isotope effect studies revealed C-H bond activation as the rate-determining step. Radical scavenging experiments indicated a radical pathway. The 1H NMR of an aliquot of reaction mixture and in situ trapping with 2-aminothiophenol revealed the formation of aldehyde during aerobic oxidation of the arylmethanes. The reaction has broad scope for different variations of the aroyl source and the directing group that includes benzothiazole, benzooxazole, pyridine, quinoxaline, pyrimidine, and azoarene. The benzylic methylene moiety was found to be the source of the aroyl carbon with the benzyl ether moiety being the most preferred followed by the carbonyl group of aryl aldehyde and the aryl methane. However, the ease of availability of aryl methanes makes them the most attractive as an aroyl source. A time dependent selective mono- and bis-aroylation can be achieved. The 1,3-diarylpyrimidines exhibited regioselective aroylation of the 2-phenyl moiety irrespective of the absence or presence of any substitutent (electron withdrawing or electron donating) in the 3-phenyl moiety. For unsymmetrical azoarenes, selective aroylation took place in the phenyl moiety bearing the substituent.
- Pipaliya, Bhavin V.,Chakraborti, Asit K.
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p. 3767 - 3780
(2017/04/11)
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- Preparation method of polysubstituted pyrimidine
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The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of polysubstituted pyrimidine. The method comprises the following step that amidine hydrochloride and a propiophenone compound react in the presence of an iron source compound, 1,10-phenanthroline and tetramethyl piperidine nitric oxide to obtain polysubstituted pyrimidine, wherein propiophenone or a propiophenone derivative is adopted as the propiophenone compound. According to the method, polysubstituted pyrimidine can be generated through a reaction by taking the propiophenone compound and amidine hydrochloride as reacting raw materials under combined promotion of the iron source compound, 1,10-phenanthroline and the tetramethyl piperidine nitric oxide; a strong alkaline or strong acidic environment is not needed, the reaction conditions are simple and mild, and the yield of polysubstituted pyrimidine is high. Experiment results show that the maximum yield of polysubstituted pyrimidine prepared through the method can reach 93% or above.
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Paragraph 0053; 0554; 0055; 0056; 0057; 0058; 0059-0063
(2017/07/26)
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- Iron Catalysis for Modular Pyrimidine Synthesis through β-Ammoniation/Cyclization of Saturated Carbonyl Compounds with Amidines
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An efficient method for the modular synthesis of various pyrimidine derivatives by means of the reactions of ketones, aldehydes, or esters with amidines in the presence of an in situ prepared recyclable iron(II)-complex was developed. This operationally simple reaction proceeded with broad functional group tolerance in a regioselective manner via a remarkable unactivated β-C-H bond functionalization. Control experiments were performed to gain deep understanding of the mechanism, and the reactions are likely to proceed through a designed TEMPO complexation/enamine addition/transient α-occupation/β-TEMPO elimination/cyclization sequence.
- Chu, Xue-Qiang,Cao, Wen-Bin,Xu, Xiao-Ping,Ji, Shun-Jun
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supporting information
p. 1145 - 1154
(2018/06/18)
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- Cu-Catalyzed [3 + 3] Annulation for the Synthesis of Pyrimidines via β-C(sp3)-H Functionalization of Saturated Ketones
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A novel, efficient, and facile approach for the synthesis of structurally important pyrimidines has been successfully developed by Cu-catalyzed and 4-HO-TEMPO-mediated [3 + 3] annulation of commercially available amidines with saturated ketones. This method provides a new protocol for the synthesis of pyrimidines by a cascade reaction of oxidative dehydrogenation/annulation/oxidative aromatization via direct β-C(sp3)-H functionalization of saturated ketones followed by annulation with amidines.
- Zhan, Jun-Long,Wu, Meng-Wei,Chen, Fei,Han, Bing
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p. 11994 - 12000
(2016/12/09)
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- Transition Metal Free Intermolecular Direct Oxidative C-N Bond Formation to Polysubstituted Pyrimidines Using Molecular Oxygen as the Sole Oxidant
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Various polysubstituted pyrimidines are smoothly formed via a base-promoted intermolecular oxidation C-N bond formation of allylic C(sp3)-H and vinylic C(sp2)-H of allyllic compounds with amidines using O2 as the sole oxid
- Guo, Wei,Li, Chunsheng,Liao, Jianhua,Ji, Fanghua,Liu, Dongqing,Wu, Wanqing,Jiang, Huanfeng
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p. 5538 - 5546
(2016/07/13)
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- Base mediated direct C-H amination for pyrimidines synthesis from amidines and cinnamaldehydes using oxygen as green oxidants
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A direct metal-free C-H amination reaction of cinnamaldehydes and amidines to realize the synthesis of polysubstituted pyrimidines was developed in the presence of base. This greener synthetic methodology provides a straightforward approach to the synthes
- Guo, Wei
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- Au(I)-catalyzed domino intramolecular cyclization for the synthesis of 2,4-disubstituted pyrimidines
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An efficient Au-catalyzed domino intramolecular cyclization reaction has been developed for the construction of pyrimidine derivatives from ynals and amidines at room temperature for 3 h. This transformation provides a new method for the formation of C-C
- Zhan, Haiying,Chen, Longbin,Tan, Jingwen,Cao, Hua
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p. 109 - 112
(2015/11/09)
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- NIS-catalyzed oxidative cyclization of alcohols with amidines: A simple and efficient transition-metal free method for the synthesis of 1,3,5-triazines
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An efficient method for the synthesis of 1,3,5-triazines by NIS-catalyzed oxidative cyclization of alcohols with amidines has been developed. The reaction works smoothly under transition-metal free and phosphine-free conditions to afford a wide range of 1,3,5-triazine derivatives in moderate to good yields. The synthetic methodology was achieved via in situ oxidation of alcohols to aldehydes.
- Tiwari, Abhishek R.,Akash,Bhanage, Bhalchandra M.
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supporting information
p. 10973 - 10976
(2015/11/25)
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- Catalytic asymmetric hydrogenation of pyrimidines
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The asymmetric hydrogenation of pyrimidines proceeded with high enantioselectivity (up to 99% ee) using an iridium catalyst composed of [IrCl(cod)]2, a ferrocene-containing chiral diphosphine ligand (Josiphos), iodine, and Yb(OTf)3 (cod=1,5-cyclooctadiene). The chiral catalyst converted various 4-substituted pyrimidines into chiral 1,4,5,6-tetrahydropyrimidines in high yield. The lanthanide triflate is crucial for achieving the high enantioselectivity as well as for activating the heteroarene substrate.
- Kuwano, Ryoichi,Hashiguchi, Yuta,Ikeda, Ryuhei,Ishizuka, Kentaro
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supporting information
p. 2393 - 2396
(2015/03/04)
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- Ruthenium-catalyzed double-fold C-H tertiary alkoxycarbonylation of arenes using di-tert-butyl dicarbonate
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An efficient ruthenium-catalyzed double-fold C-H alkoxycarbonylation of arenes was developed using di-tert-butyl dicarbonate as the tertiary esterification reagent, which leads to a direct route to valuable 2,6-dicarboxylated products. This journal is
- Hong, Xiaohu,Wang, Hao,Liu, Bingxin,Xu, Bin
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supporting information
p. 14129 - 14132
(2014/12/11)
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- Synthesis of Imidazoles and Pyrimidines Using Palladium-Catalyzed Decarboxylative Intramolecular Condensation of 1,2,4-Oxadiazol-5(4 H)-ones
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We found that 1,2,4-oxadiazol-5(4H)-ones acted as iminonitrene equivalents in the presence of a palladium catalyst and a stoichiometric amount of phosphine and that aza-Wittig-type condensation with the internal carbonyl moiety occurred to afford the corresponding imidazoles and pyrimidines. Georg Thieme Verlag Stuttgart. New York.
- Shimbayashi, Takuya,Okamoto, Kazuhiro,Ohe, Kouichi
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p. 1916 - 1920
(2014/08/18)
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- One-pot oxidation and rearrangement of propargylamines and in situ pyrazole synthesis
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Reported here are procedures for a one-pot oxidation and rearrangement of propargylamines to synthesize enaminones, with supporting mechanistic studies. Also reported are the extended one-pot syntheses of pyrazoles, including celecoxib and various heterocyclic compounds.
- Chen, Jinshan,Properzi, Roberta,Uccello, Daniel P.,Young, Jennifer A.,Dushin, Russell G.,Starr, Jeremy T.
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p. 4146 - 4149
(2014/09/29)
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- Copper(II)-catalyzed synthesis of pyrimidines from propargylic alcohols and amidine: A propargylation-cyclization-oxidation tandem reaction
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A new approach to the tandem synthesis of 2,4-disubstituted or 2,4,6-trisubstituted pyrimidines from propargylic alcohols with amidine is described. This reaction is catalyzed by 20 mol% Cu(OTf)2 to give pyrimidines in moderate to good yields v
- Lin, Min,Chen, Qing-Zhen,Zhu, Yu,Chen, Xin-Liang,Cai, Ji-Jun,Pan, Ying-Ming,Zhan, Zhuang-Ping
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experimental part
p. 1179 - 1183
(2011/06/26)
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- Palladium-Catalyzed Regioselective C-H Bond ortho-Acetoxylation of Arylpyrimidines
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An efficient and regioselective palladium-catalyzed ortho C-H acetoxylation reaction was developed to afford, ortho monoacetoxylated arylpyrimidmes in good to excellent yields by using cupric trifluoroacetate as a cocatalyst. A wide variety of oxygenated
- Zheng, Xiaojian,Song, Bingrui,Xu, Bin
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supporting information; experimental part
p. 4376 - 4380
(2010/10/04)
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- Palladium-catalyzed monoselective halogenation of C-H bonds: Efficient access to halogenated arylpyrimidines using calcium halides
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A wide variety of ortho-halogenated arylpyrimidines were prepared with high monoselectivity and functional-group tolerance by using calcium halides as crucial halogenating agents and cupric trifluoroacetate as oxidant in the presence of air.
- Song, Bingrui,Zheng, Xiaojian,Mo, Jun,Xu, Bin
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supporting information; experimental part
p. 329 - 335
(2010/04/28)
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- Barium manganate in microwave-assisted oxidation reactions: synthesis of solvatochromic 2,4,6-triarylpyrimidines
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Synthesis of 2,4,6-trisubstituted pyrimidines by tandem oxidation/heterocyclocondensation of propargylic alcohols and amidines is effected rapidly and efficiently under microwave dielectric heating using barium manganate as oxidant. Irradiation at 150 °C
- Bagley, Mark C.,Lin, Zhifan,Pope, Simon J.A.
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experimental part
p. 6818 - 6822
(2010/04/27)
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- Microwave-assisted, efficient and regioselective Pd-catalyzed C-phenylation of halopyrimidines
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We herein report that flash heating microwave irradiation is a helpful tool in the formation of arylpyrimidines from the corresponding halopyrimidines. The palladium-catalyzed cross-coupling reactions of 2,4-di- and 2,4,5-trihalopyrimidines with phenylboronic acid under the above conditions are described. By use of the appropriate catalyst and the adequate halopyrimidine, good regioselectivity can be achieved in the 2-, 4-, or 5-positions of the heterocycle. In addition, we show that this methodology is ameneable for the stepwise preparation of mono-, di-, and triphenylpyrimidines.
- Ceide, Susana Conde,Montalban, Antonio Garrido
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p. 4415 - 4418
(2007/10/03)
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- Aryl-aryl bonds formation in pyridine and diazine series. Diazines part 41
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The synthesis of several symmetrical polyaromatic compounds with pyridine or diazine units has been achieved by homocoupling of aryl halides with Pd(OAc)2 as catalyst. Cross-coupling reactions of aryl Grignard reagents with Fe(acac)3 as catalyst allowed the synthesis of various unsymmetrical polyaryl- or polyheteroaryl compounds with π-deficient rings.
- Boully, Ludovic,Darabantu, Mircea,Turck, Alain,Ple, Nelly
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p. 1423 - 1428
(2007/10/03)
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- One-pot synthesis of pyridines or pyrimidines by tandem oxidation-heteroannulation of propargylic alcohols
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Pyridines and pyrimidines are prepared in a single step from propargylic alcohols by in situ oxidation with o-iodoxybenzoic acid or manganese dioxide and reaction with enamines or amidines, respectively, under either thermal or microwave-assisted conditions in a new one-pot tandem oxidation-heteroannulation procedure. The reaction of a β-ketoester, propargylic alcohol and ammonium acetate, with in situ oxidation, constitutes a highly facile three-component reaction for the synthesis of pyridines that accomplishes four distinct synthetic operations in one-pot, good yield and with total regiocontrol.
- Bagley, Mark C.,Hughes, David D.,Sabo, Halima M.,Taylor, Paul H.,Xiong, Xin
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p. 1443 - 1446
(2007/10/03)
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- Traceless solid phase synthesis of 2-substituted pyrimidines using an 'off-the-shelf' chlorogermane-functionalised resin
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The parallel solid phase synthesis of an 18-member library of 2-substituted pyrimidines is described using a chlorogermane-functionalised resin. The success of the key Pinner-type condensations between a resin-bound enaminone and an array of amidine hydrochlorides highlights the stability of arylgermane linkers (cf. arylsilanes) towards strongly basic/nucleophilic conditions.
- Spivey, Alan C.,Srikaran, Ratnasothy,Diaper, Christopher M.,Turner, David J.
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p. 1638 - 1640
(2007/10/03)
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- Highly efficient synthesis of pyrimidines under microwave-assisted conditions
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Microwave irradiation of an amidine and alkynone in acetonitrile at 120°C gives 2,4-disubstituted and 2,4,6-trisubstituted pyrimidines in very high yield.
- Bagley, Mark C.,Hughes, David D.,Taylor, Paul H.
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p. 259 - 261
(2007/10/03)
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- Arylation of halogenated pyrimidines via a suzuki coupling reaction
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The Suzuki coupling reaction has been used extensively for the synthesis of a wide variety of unsymmetrical biaryl compounds. We have extended this reaction to demonstrate the utility of preparing monophenyl-, diphenyl-, or triphenylpyrimidine depending on the reaction conditions. Further, it has been shown that chloropyrimidine substrates are preferable over iodo-, bromo-, or fluoropyrimidines.
- Schomaker,Delia
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p. 7125 - 7128
(2007/10/03)
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- Synthesis of indolylpyrimidines via cross-coupling of indolylboronic acid with chloropyrimidines facile synthesis of meridianin D
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Palladium catalyzed cross-coupling reaction of 3-indolylboronic acid with 2,4-dichloropyrimidines proceeded regioselectively to yield indolyl-or bis(indolyl)pyrimidines in high yield, depending on the projection of 3indolylboronic acid. The marine indole alkaloid meridianin D and an analogue were synthesised via the palladium catalyzed cross-coupling reaction as a key step.
- Jiang, Biao,Yang, Cai-Guang
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p. 1489 - 1498
(2007/10/03)
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- Reaction of 2-Dimethylaminomethylene-1,3-diones with Dinucleophiles. VIII. Synthesis of Ethyl and Methyl 2,4-Disubstituted 5-Pyrimidinecarboxylates
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Reaction of ethyl or methyl 2-dimethylaminomethylene-3-oxoalkanoates with N-C-N dinucleophiles such as guanidine, acetamidine or benzamidine afforded in high yields the relative esters of 4-substituted 2-amino-, 2-methyl- or 2-phenyl-5-pyrimidinecarboxylic acids, respectively.These esters were hydrolyzed to the corresponding carboxylic acids, which were converted by heating to 4-substituted 2-pyrimidinamines, 2-methyl or 2-phenylpyrimidines, respectively, generally in excellent yields.The 4-unsubstituted ethyl 2-amino-, 2-methyl- and 2-phenyl-5-pyrimidinecarboxylateswere obtained in moderate yields by reaction of the above dinucleophiles with ethyl 2,2-diformylacetate.These esters were hydrolyzed and the corresponding acids (with the exception of the 2-methyl derivative) were decarboxylated to give 2-pyrimidinamine and 2-phenylpyrimidine in satisfactory yields.
- Schenone, Pietro,Sansebastiano, Laura,Mosti, Luisa
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p. 295 - 305
(2007/10/02)
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