- Hydrazine Hydrate Accelerates Neocuproine–Copper Complex Generation and Utilization in Alkyne Reduction, a Significant Supplement Method for Catalytic Hydrogenation
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Diimine (HN═NH) is a strong reducing agent, but the efficiency of diimine oxidized from hydrazine hydrate or its derivatives is still not good enough. Herein, we report an in situ neocuproine–copper complex formation method. The redox potential of this complex enable it can serve as an ideal redox catalyst in the synthesis of diimine by oxidation of hydrazine hydrate, and we successfully applied this technique in the reduction of alkynes. This reduction method displays a broad functional group tolerance and substrate adaptability as well as the advantages of safety and high efficiency. Especially, nitro, benzyl, boc, and sulfur containing alkynes can be reduced to the corresponding alkanes directly, which provides a useful complementary method to traditional catalytic hydrogenation. Besides, we applied this method in the preparation of the Alzheimer’s disease drug CT-1812 and studied the mechanism.
- Chen, Guoliang,He, Xiaoyan,Huang, Gang,Lu, Xiuhong,Wang, Jincheng,Yang, Zhenjiao,Zhang, Yongsheng,Zhang, Zeng
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p. 17696 - 17709
(2021/12/09)
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- Base-Catalyzed Borylation/B-O Elimination of Propynols and B2pin2 Delivering Tetrasubstituted Alkenylboronates
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An efficient approach to tetrasubstituted alkenylboronates via a cascade borylation/B-O elimination of propynols and B2pin2 was disclosed. A series of tetrasubstituted alkenylboronates were readily furnished with this strategy in good yields, with further transformations leading to tetrasubstituted alkenes and β-diketones demonstrating the synthetic potential of the alkenylboronates constructed by this strategy as versatile intermediates in organic synthesis.
- Kuang, Zhijie,Chen, Haohua,Yan, Jianxiang,Yang, Kai,Lan, Yu,Song, Qiuling
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supporting information
p. 5153 - 5157
(2018/09/12)
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- Palladium-Catalyzed Nitration of Meyer-Schuster Intermediates with tBuONO as Nitrogen Source at Ambient Temperature
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A novel domino palladium-catalyzed nitration of Meyer-Schuster intermediates which were generated in situ from propargylic alcohols was developed, by the use of t-BuONO, leading to α-nitro enones in good to excellent yields at room temperature with a broa
- Lin, Yuanguang,Kong, Weiguang,Song, Qiuling
-
supporting information
p. 3702 - 3705
(2016/08/16)
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- Palladium-catalyzed oxidative deacetonative coupling of 4-aryl-2-methyl-3-butyn-2-ols with H-phosphonates
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An efficient and generally applicable protocol for palladium-catalyzed oxidative deacetonative coupling of 4-aryl-2-methyl-3-butyn-2-ols with dialkyl H-phosphonates has been developed. This methodology provides a new and practical route to alkynylphosphonates using the inexpensive 4-aryl-2-methyl-3-butyn-2-ols as the alkyne sources. This reaction could also be performed with aryl bromides, 2-methyl-3-butyne-2-ol and dialkyl H-phosphonates using the cheap 2-methyl-3-butyne-2-ol as an alkyne source. This journal is
- Li, Xiang,Sun, Suyan,Yang, Fan,Kang, Jianxun,Wu, Yusheng,Wu, Yangjie
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p. 2432 - 2436
(2015/03/04)
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- Synthesis of Oxazolidin-2-ones by Tandem Cyclization of Propargylic Alcohols and Phenyl Isocyanate Promoted by Silver Catalysts as π-Lewis Acids
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Highly Z-selective syntheses of oxazolidin-2-ones from propargylic alcohols containing internal alkynes and phenyl isocyanate were achieved by using a combination of silver acetate and N,N-dimethylaminopyridine. The catalytic system was applied to proparg
- Sekine, Kohei,Mawatari, Takanori,Yamada, Tohru
-
supporting information
p. 2447 - 2450
(2015/10/19)
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- Tandem C-2 functionalization-intramolecular Azide-Alkyne 1,3-Dipolar Cycloaddition reaction: A convenient route to highly diversified 9H-Benzo[b]pyrrolo[1,2-g][1,2,3]triazolo[1,5-d][1,4]diazepines
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An efficient diversity-oriented synthetic approach to annulated 9H-benzo[b]pyrrolo[1,2-g][1,2,3]- triazolo[1,5-d][1,4]diazepines has been developed using a Sc(OTf)3-catalyzed two-component tandem C-2 functionalization- intramolecular azide-alky
- Hussain, Mohd. Kamil,Ansari, Mohd. Imran,Kant, Ruchir,Hajela, Kanchan
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supporting information
p. 560 - 563
(2014/04/03)
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- Sonogashira reaction of aryl and heteroaryl halides with terminal alkynes catalyzed by a highly efficient and recyclable nanosized MCM-41 anchored palladium bipyridyl complex
-
A heterogeneous catalyst, nanosized MCM-41-Pd, was used to catalyze the Sonogashira coupling of aryl and heteroaryl halides with terminal alkynes in the presence of CuI and triphenylphosphine. The coupling products were obtained in high yields using low Pd loadings to 0.01 mol%, and the nanosized MCM-41-Pd catalyst was recovered by centrifugation of the reaction solution and re-used in further runs without significant loss of reactivity.
- Lin, Bo-Nan,Huang, Shao-Hsien,Wu, Wei-Yi,Mou, Chung-Yuan,Tsai, Fu-Yu
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experimental part
p. 9157 - 9173
(2011/02/27)
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- UC Pd: A new form of PdVC for sonogashira couplings
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Screening of different sources of Pd/C shows reagents of highly variable nanoparticle sizes and oxidation states of the metal. Typically, catalysts with higher surface area are viewed as likely to be the more reactive. In this paper a new form of Pd/C, "U
- Duplais, Christophe,Forman, Arnold J.,Baker, Benjamin A.,Lipshutz, Bruce H.
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supporting information; experimental part
p. 3366 - 3371
(2010/06/21)
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- Fast copper-, ligand- and solvent-free Sonogashira coupling in a ball mill
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A solvent-free method for the Sonogashira coupling reaction was established under ball milling conditions without the use of copper or additional ligands. Pd(OAc)2 or Pd(PPh3)4 in combination with 1,4-diazabicyclo[2.2.2]octane (DABCO) were chosen as catalysts and base, respectively. The reaction was investigated using a variety of aryl halides and acetylenes and with different amounts of the Pd-catalyst and DABCO. Results indicated that the employment of Pd(OAc)2 in combination with SiO2 as a grinding auxiliary preferentially induces the transformation of aryl iodides to the corresponding Sonogashira coupling products. In contrast, both the substitution of SiO2 by Al 2O3 or replacement of Pd(OAc)2 with Pd(PPh 3)4 enable the reaction of aryl bromides with phenylacetylenes. The selective reaction of bis-ethynyl compounds to double-coupled products and the influence of further common bases on the reaction was also scrutinized, confirming the high reactivity of DABCO as a base for solvent-free transformations.
- Thorwirth, Rico,Stolle, Achim,Ondruschka, Bernd
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supporting information; experimental part
p. 985 - 991
(2010/07/14)
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- Copper-free Sonogashira coupling in amine-water solvent mixtures
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Extensive study of different amine-water solvent mixtures was carried out for copper free Sonogashira coupling of aryl iodides. The influence of the palladium sources, ligands, amine-water ratio and further additives was also evaluated. Application of sec-butylamine-water mixture proved to be an excellent medium for rapid and efficient coupling of aryl-iodides at ambient temperature in the presence of PdCl2(PPh3)2 as catalyst.
- Komáromi, Anna,Tolnai, Gergely László,Novák, Zoltán
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scheme or table
p. 7294 - 7298
(2009/04/11)
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- SUBSTITUTED ETHYNYL GOLD-NITROGENATED HETEROCYCLIC CARBENE COMPLEX AND ORGANIC ELECTROLUMINESCENT DEVICE USING SAME
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The present invention provides a substituted ethynyl gold-nitrogen containing heterocyclic carbene complex represented by the general formula (1): wherein L represents a nitrogen containing heterocyclic carbene ligand; and X represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group; in which one or more hydrogen atoms on the carbon atom(s) of X may be replaced by a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a dialkylamino group, an acyl group or an arylcarbonyl group; and, when more than one hydrogen atom on the carbon atom(s) of X is replaced by the alkyl group, the alkenyl group, the aryl group, the aralkyl group, the alkoxy group, the aryloxy group, the dialkylamino group, the acyl group or the arylcarbonyl group, the adjacent groups may be bonded together to form a ring, a method for preparing the same, and an organic electroluminescent device comprising the substituted ethynyl gold-nitrogen containing heterocyclic carbene complex in at least one organic compound thin layer.
- -
-
Page/Page column 55
(2008/06/13)
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- A simple and efficient copper-free catalytic system based on a palladacycle for the arylation of alkynes
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The palladacycle [Pd(k2-C,N-C=(C6H 5)C(Cl)CH2NMe2)(μ-Cl)]2 (1) derived from the chloropalladation of 3-(dimethylamino)-1-phenyl-1-propyne and its phosphine adduct [Pd(k2-C,N-C=(C6H5)C(Cl) CH2NMe2)P(4-CF3C6H4) 3(Cl)] (3) promote the alkynylation of bromo- and iodoarenes under relatively mild reaction conditions. The coupling of iodoarenes and activated bromoarenes with terminal alkynes can be conducted at room temperature. Turnover numbers have been achieved up to 105 with iodoarenes and up to 94 for deactivated bromoarenes but at higher temperatures (120°C). Selective poisoning experiments (Hg, Collman and Crabtree tests) suggest that soluble Pd(0) species are the most probable catalytically active species involved in this Csp2-Csp coupling reaction.
- Consorti, Crestina S.,Flores, Fabricio R.,Rominger, Frank,Dupont, Jairton
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p. 133 - 141
(2007/10/03)
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- Phosphorinanes as ligands for palladium-catalyzed cross-coupling chemistry
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(Chemical Equation Presented) Phosphorinanes are presented as a class of phosphine ligand suitable for organopalladium cross-coupling chemistry. Prepared via a direct double Michael addition of a monoalkyl- or arylphosphine to phorone followed by a Wolf-K
- Brenstrum, Tim,Clattenburg, Julie,Britten, James,Zavorine, Serguei,Dyck, Jeff,Robertson, Alan J.,McNulty, James,Capretta, Alfredo
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p. 103 - 105
(2007/10/03)
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- High throughput evaluation of the production of substituted acetylenes by the Sonogashira reaction followed by the Mizoroki-Heck reaction in ionic liquids, in situ, using a novel array reactor
-
The parallel Sonogashira coupling reaction was carried out under copper-free condition by integrating the advantages of ionic liquids as the reaction media followed by the simultaneous-multiple Mizoroki-Heck reaction in situ by the use of a novel array re
- Rahman, Md. Taifur,Fukuyama, Takahide,Ryu, Ilhyong,Suzuki, Kanae,Yonemura, Koichi,Hughes, Philip F.,Nokihara, Kiyoshi
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p. 2703 - 2706
(2007/10/03)
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- A convenient high activity catalyst for the Sonogashira coupling of aryl bromides
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A mixture of Na2PdCl4, CuI and (t-Bu) 3PH+BF4- (molar ratio 4:3:8) dispersed in H2N(i-Pr)2 Br can be used as a "single source" precatalyst for the Sonogashira coupling of aryl bromides with various aryl- and alkylacetylenes in HN(i-Pr)2 solvent. Arylacetylenes require just 0.005 mol % of Pd catalyst at 80°C, with TOFs ranging between 3,200 and 10,000 h-1.
- Koellhofer, Axel,Plenio, Herbert
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p. 1295 - 1300
(2007/10/03)
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- Pd/C-mediated coupling of aryl halides with terminal alkynes in water
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2-Aminoethanol facilitated the alkynylation of aryl halides (Sonogashira reaction) under palladium/charcoal-copper catalysis in water affording a mild and practical method for the synthesis of arylalkynes. A variety of terminal alkynes were coupled with a
- Batchu, Venkateswara Rao,Subramanian, Venkataraman,Parasuraman, Karuppasamy,Swamy, Nalivela Kumara,Kumar, Sanjeev,Pal, Manojit
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p. 9869 - 9877
(2007/10/03)
-
- Palladium complexes of 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phenyl-6- phosphaadamantane: Synthesis, crystal structure and use in the Suzuki and Sonogashira reactions and the α-arylation of ketones
-
Palladium complexes of 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phenyl-6- phosphaadamantane were prepared and characterized with Pd[1,3,5,7-tetramethyl-2, 4,8-trioxa-6-phenyl-6-phosphaadamantane]2·dba shown to be an effective catalyst for use in the
- Adjabeng, George,Brenstrum, Tim,Frampton, Christopher S.,Robertson, Al J.,Hillhouse, John,McNulty, James,Capretta, Alfredo
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p. 5082 - 5086
(2007/10/03)
-
- Coupling reactions of aryl bromides with 1-alkynols catalysed by a tetraphosphine/palladium catalyst
-
cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/ [PdCl(C3H5)]2 system catalyses efficiently the coupling reactions of aryl halides with a variety of alkynols such as propargyl alcohol, but-1-yn-4-ol, pent
- Feuerstein, Marie,Doucet, Henri,Santelli, Maurice
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p. 1603 - 1606
(2007/10/03)
-
- PMHS-mediated couplings of alkynes or benzothiazoles with various electrophiles: Application to the synthesis of (-)-akolactone A
-
Polymethylhydrosiloxane (PMHS) in combination with CsF facilitates the cross-coupling of alkynes or benzothiazoles with an array of vinyl, styryl, and aryl halides or nonaflates as well as acid chlorides. Experimental and spectroscopic evidence indicates that these reactions involve the in situ generation of a siloxyl intermediate. These cross-couplings proceed relatively quickly at room temperature and under amine-free conditions. To demonstrate the applicability of the method, a total synthesis of the cyctotoxic butanolide (-)-akolactone A was carried out.
- Gallagher, William P.,Maleczka Jr., Robert E.
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p. 6775 - 6779
(2007/10/03)
-
- Polymethylhydrosiloxane (PMHS) as an additive in Sonogashira reactions
-
Polymethylhydrosiloxane (PMHS) in combination with CsF facilitates the Sonogashira reaction of a variety of alkynes and electrophiles. These couplings appear to involve the in situ formation and reaction of an alkynylsiloxane. Such couplings can be run am
- Gallagher, William P.,Maleczka Jr., Robert E.
-
p. 537 - 541
(2007/10/03)
-
- Efficient and General Protocol for the Copper-Free Sonogashira Coupling of Aryl Bromides at Room Temperature
-
(Equation presented) A mild and general protocol for the copper-free Sonogashira coupling of aryl bromides with acetylenes has been developed. The use of (AllylPdCl)2 and P(t-Bu)3 provides the active Pd(0) catalyst that allows subseq
- Soheili, Arash,Albaneze-Walker, Jennifer,Murry, Jerry A.,Dormer, Peter G.,Hughes, David L.
-
p. 4191 - 4194
(2007/10/03)
-
- Sonogashira coupling using bulky palladium-phenanthryl imidazolium carbene catalysis
-
(Matrix presented) Bulky phenanthracenyl imidazolium-derived carbene ligands were investigated for copper-free Sonogashira coupling with terminal acetylenes. Aryl bromides and iodides gave coupled products in excellent yields from the Pd(PPh3)2Cl2 complex with potassium t-butoxide and 18-crown-6 in THF. A remarkable dependence on the size of the ligand was found. The highest yields were obtained with the bulky 2,9-dicyclohexyl-10-phenanthryl ligand 5.
- Ma, Yudao,Song, Chun,Jiang, Wei,Wu, Quansheng,Wang, Yong,Liu, Xueying,Andrus, Merritt B.
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p. 3317 - 3319
(2007/10/03)
-
- An easily accessible resin-supported palladium catalyst for Sonogashira coupling
-
Readily available aminomethyl-polystyrene beads can be transformed in a one-pot reaction to an air-stable polymer-bound chelate phosphine, which can be used for the immobilization of homogeneous catalysts. Such prepared Pd catalysts have proven to be useful reagents for mediating Sonogashira-coupling reactions.
- Gonthier, Elisabeth,Breinbauer, Rolf
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p. 1049 - 1051
(2007/10/03)
-
- Application of the fluorous-biphase concept to palladium-catalyzed Sonogashira couplings
-
Sonogashira C,C couplings in a fluorous biphasic system by application of three differently perfluorotagged Pd complexes are reported. All three complexes were probed in the coupling of four bromoarenes to three alkynes. The parallel workup procedure allo
- Markert, Christian,Bannwarth, Willi
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p. 1877 - 1882
(2007/10/03)
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- Pd(PhCN)2Cl2/P(t-Bu)3: A versatile catalyst for Sonogashira reactions of aryl bromides at room temperature
-
(matrix presented) Pd(PhCN)2Cl2/P(t-Bu)3 serves as an efficient and a versatile catalyst for room-temperature Sonogashira reactions of aryl bromides.
- Hundertmark, Thomas,Littke, Adam F.,Buchwald, Stephen L.,Fu, Gregory C.
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p. 1729 - 1731
(2007/10/03)
-