- Ultra-small Pd(0) nanoparticles into a designed semisynthetic lipase: An efficient and recyclable heterogeneous biohybrid catalyst for the heck reaction under mild conditions
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A novel heterogeneous enzyme-palladium (Pd) (0) nanoparticles (PdNPs) bionanohybrid has been synthesized by an efficient, green, and straightforward methodology. A designed Geobacillus thermocatenulatus lipase (GTL) variant genetically and then chemically
- Lopez-Tejedor, David,De Las Rivas, Blanca,Palomo, Jose M.
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- Efficient Synthesis of Polysubstituted Furans through a Base-Promoted Oxacyclization of (Z)-2-En-4-yn-1-ols
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An efficient base catalyzed oxacyclization of Z-enynols has been developed under transition metal-free reaction conditions, thus resulting in a variety of new di-, tri-, and tetra-substituted furans. This approach allowed us to obtain 32 new compounds. Furthermore, DFT calculations were realized to depict a relationship between the natural population analysis and experimental results with alkyl or aryl groups for the synthesis of 2-benzylfuran. A one-pot Sonogashira/oxacyclization approach offers a flexible, robust and efficient alternative to base catalyzed cyclization is also carried out.
- Hrizi, Asma,Thiery, Emilie,Romdhani-Younes, Moufida,Jacquemin, Johan,Thibonnet, Jér?me
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supporting information
p. 3798 - 3806
(2021/06/14)
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- One-pot synthesis of 3-substituted-4H-[1,2,3] triazolo[5,1-c][1,4]oxazin-6(7H)-ones from propargyl alcohols, chloroacetyl chloride, and sodium azide
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An efficient, one-pot synthesis of 3-substituted-4H-[1,2,3]triazolo[5,1-c][1,4]oxazin-6(7H)-ones is developed via sequential esterification, substitution, and 1,3-dipolar cycloaddition processes of various propargyl alcohols, chloroacetyl chloride, and so
- Chen, Jun-Min,Liu, Xiao-Ling,Sheng, Shou-Ri,Wei, Mei-Hong,Zhang, Xiao-Lan
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p. 482 - 485
(2020/11/30)
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- Bi(OTf)3-catalyed One-pot Synthesis of α-Halo-β-amino Ketones and Acyl Aziridines from 3-Aryl Propargyl Alcohols
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A Bi(OTf)3-catalyed reaction of 3-aryl propargyl alcohols with sulfonamide and halogen source was firstly investigated, which provided a facile route for the synthesis of a large variety of α-halo-β-amino ketones. The key intermediates, β-amino
- Zhang, Qinglin,Duan, Yongbin,Guo, Huifeng,Yang, Hong,Zhai, Jiulong,Li, Tiantian,Wang, Zhihai,Lu, Xiaolei,Wang, Yan,Yin, Yan
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supporting information
p. 1832 - 1838
(2021/06/09)
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- RET INHIBITORS, PHARMACEUTICAL COMPOSITIONS AND USES THEREOF
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Provided herein are a RET inhibitor, a pharmaceutical composition thereof and uses thereof. In particular, provided is a compound having Formula (I) or a stereoisomer, a geometric isomer, a tautomer, an N-oxide, a solvate, a metabolite, a pharmaceutically acceptable salt or a prodrug thereof. Provided is a pharmaceutical composition comprising the compound, and uses of the compound and pharmaceutical composition thereof for the preparation of a medicament, in particular for treatment and prevention of RET-related diseases and conditions, including cancer, irritable bowel syndrome, and/or pain associated with irritable bowel syndrome.
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Paragraph 00410
(2020/07/06)
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- RET INHIBITORS, PHARMACEUTICAL COMPOSITIONS AND USES THEREOF
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Provided herein are a RET inhibitor, a pharmaceutical composition thereof and uses thereof. In particular, provided is a compound having Formula (I) or a stereoisomer, a geometric isomer, a tautomer, an N-oxide, a solvate, a metabolite, a pharmaceutically acceptable salt or a prodrug thereof. Provided is a pharmaceutical composition comprising the compound, and uses of the compound and pharmaceutical composition thereof for the preparation of a medicament, in particular for treatment and prevention of RET-related diseases and conditions, including cancer, irritable bowel syndrome, and/or pain associated with irritable bowel syndrome.
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Paragraph 00230; 00624
(2020/07/05)
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- Integrating Reactors and Catalysts through Three-Dimensional Printing: Efficiency and Reusability of an Impregnated Palladium on Silica Monolith in Sonogashira and Suzuki Reactions
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For this work, an integrated system composed of a polypropylene reactor and a palladium on silica monolithic catalyst was designed and manufactured by 3D-printing. These devices are able to perform solution phase chemistry in a robotic orbital shaker. The capped reactor was obtained in its entirety by 3D-printing, using polypropylene and fused deposition modeling. The monolithic catalyst was also obtained by 3D-printing -robocasting- of a silica support, sintering and subsequent palladium deposition through the wet impregnation method. The catalytic efficiency in Sonogashira or Suzuki reactions as well as the recyclability of the entire system – catalyst+reactor – were studied. The strong electrostatic adsorption (SEA) of the palladium on sintered silica and the reduced mechanical stress produced by the convenient adjustment of the catalyst into the polypropylene reactor makes the catalytic system reusable without significant loss of catalytic activity.
- Díaz-Marta, Antonio S.,Ya?ez, Susana,Lasorsa, Eliana,Pacheco, Patricia,Tubío, Carmen R.,Rivas, José,Pi?eiro, Yolanda,Gómez, Manuel A. Gonzalez,Amorín, Manuel,Guitián, Francisco,Coelho, Alberto
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p. 1762 - 1771
(2020/02/15)
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- Regioselective Iron-Catalysed Cross-Coupling Reaction of Aryl Propargylic Bromides and Aryl Grignard Reagents
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An iron-catalysed Kumada-type cross-coupling reaction between aryl substituted propargylic bromides and arylmagnesium reagents has been developed. Propargylic coupling products were the main or only outcome, and propargyl/allene regioselectivity was shown to depend on the electronic nature of the substituents on the triple bond of the substrate and on the arylmagnesium halide. Best selectivities were observed when electron donating substituents were present in either reagent. The process is stereoespecific, occurs with configuration inversion and no carbon-based radicals seem to be involved in the mechanism. (Figure presented.).
- Manjón-Mata, Inés,Quirós, M. Teresa,Bu?uel, Elena,Cárdenas, Diego J.
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supporting information
p. 146 - 151
(2019/12/11)
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- Regiodivergent Hydration-Cyclization of Diynones under Gold Catalysis
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Skipped diynones, efficiently prepared from biomass-derived ethyl lactate, undergo a tandem hydration-oxacyclization reaction under gold(I) catalysis. Reaction conditions have been developed for a switchable process that allows selective access to 4-pyrones or 3(2H)-furanones from the same starting diynones. Further application of this methodology in the total synthesis of polyporapyranone B was demonstrated.
- Mu?oz, Miguel A.,Sanz, Roberto,Solas, Marta,Suárez-Pantiga, Samuel
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supporting information
p. 7681 - 7687
(2020/10/12)
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- Base-induced Sommelet–Hauser rearrangement of N-(α-(2-oxyethyl)branched)benzylic glycine ester-derived ammonium salts via a chelated intermediate
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The base-induced Sommelet–Hauser (S–H) rearrangement of N-(α-branched)benzylic glycine ester-derived ammonium salts 1 was investigated. When the α-branched substituent was a simple alkyl, such as a methyl or butyl, desired S–H rearrangement product 2 was obtained in low yield with formation of the [1,2] Stevens rearranged 4 and Hofmann eliminated products 5 and 6. However, when the α-branched substituent had a 2-oxy moiety, such as 2-acetoxyethyl or 2-benzoyloxyethyl, the yields of 2 were improved. These results could be explained by formation of chelated intermediate C that stabilizes the carbanionic ylide, and the subsequent initial dearomative [2,3] sigmatropic rearrangement would be accelerated. The existence of C was supported by mechanistic experiments. This enhancement effect is not very strong or effective; however, it will expand the synthetic usefulness of ammonium ylide rearrangements.
- Baba, Souya,Hirano, Kazuki,Tayama, Eiji
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supporting information
(2020/03/13)
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- Magnetic covalent hybrid of graphitic carbon nitride and graphene oxide as an efficient catalyst support for immobilization of Pd nanoparticles
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For the first time a magnetic carbon based hybrid catalyst, Pd@g-C3N4-Fe-GO, is prepared through covalent conjugation of magnetic graphitic carbon nitride and graphene oxide followed by incorporation of Pd nanoparticles. First, the formation of the catalyst was confirmed via XRD, TG, BET, TEM, FTIR, ICP and VSM analyses and then its catalytic activity for promoting Suzuki and Sonogashira coupling reactions under mild reaction condition was investigated. To elucidate whether hybridization of two carbon materials could improve the catalytic activity, the catalytic activity of the catalyst was compared with the control catalysts (Pd@g-C3N4 -GO, Pd@g-C3N4-Fe, Pd@ Fe-GO, Pd@g-C3N4, Pd@GO and the GO/g-C3N4 physical hybrid). Moreover, the role of magnetic nanoparticles in the catalytic performance was confirmed. Notably, the catalytic activities of the catalyst and the control sample prepared via physical hybridization of two carbon materials were compared to confirm the effect of covalent conjugation on the catalytic activity. Moreover, the study of the substituent effect of p-substituted phenyl iodides was considered by Hammett plot, which revealed a beneficial effect of electron-withdrawing side groups for the C–C coupling reaction. Finally, the recyclability of Pd@g-C3N4-Fe-GO as well as leaching of Pd and magnetic nanoparticles was studied.
- Sadjadi, Samahe,Malmir, Masoumeh,Heravi, Majid M.,Ghoreyshi Kahangi, Fatemeh
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- Pd@GO/Fe3O4/PAA/DCA: a novel magnetic heterogeneous catalyst for promoting the Sonogashira cross-coupling reaction
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A hybrid system involving graphene oxide (GO), magnetic oxide (Fe3O4), acrylamide and dicyandiamide was prepared via amine functionalization of GO/Fe3O4 by means of covalent bonding with acrylamide and subsequent reaction with dicyandiamide to provide a multinitrogen containing polymer on the surface of GO. This hybrid system was utilized as a heterogeneous catalyst support for immobilizing Pd nanoparticles to provide the hybrid, Pd@GO/Fe3O4/PAA/DCA. This nano-Pd composite was characterized using Fourier transform infrared, transmission electron microscopy, scanning electron microscopy, vibrating sample magnetometer, thermogravimetric analysis, X-ray diffraction, and ICP techniques and used for promoting Sonogashira cross-coupling under mild reaction conditions. This heterogeneous and magnetic catalyst was easily separated by external magnet and was reused in a model reaction, efficiently up to six times with slight loss of catalytic activity and Pd leaching, showing the suitability of GO/Fe3O4/PAA/DCA for embedding Pd nanoparticles. To check the effect of the number of surface nitrogens of the polymeric chain on the catalytic performance, the activity of the catalyst was compared with Pd@GO/Fe3O4/PAA; increased number of the surface nitrogens on the chain polymer leads to higher loading of Pd and lower the Pd leaching.
- Daraie, Mansoureh,Heravi, Majid M.,Kazemi, Shaghayegh Sadat
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p. 2279 - 2293
(2019/08/07)
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- Rearrangement of Threonine- And Serine-Based N-(3-Phenylprop-2-yn-1-yl) Sulfonamides Yields Chiral Pyrrolidin-3-ones
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N-(3-Phenylprop-2-yn-1-yl)-sulfonamides derived from serine and threonine were synthesized using solid-phase synthesis and subjected to reaction with trimethylsilyl trifluoromethanesulfonate (TMSOTf). In contrast to the previously reported formation of 1,
- Králová, Petra,Maloň, Michal,Pospí?il, Ji?í,Soural, Miroslav
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- Pd(0) nanoparticles immobilized on multinitrogen functionalized halloysite for promoting Sonogashira reaction: studying the role of the number of surface nitrogens in catalytic performance
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Halloysite nanoclay, Hal, was amine-functionalized and subsequently reacted with 2,4,6-trichloro-1,3,5-triazine, TCT, and ethylenediamine, EDA, to provide multinitrogen containing functionality on the surface of Hal. The resulting surface-modified Hal, Ha
- Sadjadi, Samahe,Heravi, Majid M.,Masoumi, Baharak,Kazemi, Shaghayegh Sadat
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p. 119 - 134
(2019/01/30)
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- Palladium-catalyzed Sonogashira coupling reactions in γ-valerolactone-based ionic liquids
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It was demonstrated that the γ-valerolactone-based ionic liquid, tetrabutylphosphonium 4-ethoxyvalerate as a partially bio-based solvent can be utilized as alternative reaction medium for copper- and auxiliary base-free Pd-catalyzed Sonogashira coupling reactions of aryl iodides and functionalized acetylenes under mild conditions. Twenty-two cross-coupling products were isolated with good to excellent yields (72–99%) and purity (>98%). These results represent an example which proves that biomass-derived safer solvents can be utilized efficiently in common, industrially important transformations exhibiting higher chemical and environmental efficiency.
- Orha, László,Tukacs, József M.,Kollár, László,Mika, László T.
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supporting information
p. 2907 - 2913
(2019/12/14)
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- Halloysite nanoclay decorated with 2-amino pyrimidine functionalized poly glycidyl methacrylate: An efficient support for the immobilization of Pd nanoparticles
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Taking advantage of the synergistic effects between polymer (P) and halloysite clay (Hal) as well as the capability of heteroatom-containing polymers for anchoring nanoparticles and suppressing their leaching, a novel support composed of Hal and 2-amino p
- Sadjadi, Samahe,Koohestani, Fatemeh,Bahri-Laleh, Naeimeh,Didehban, Khadijeh
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- Atom-Economical Ni-Catalyzed Diborylative Cyclization of Enynes: Preparation of Unsymmetrical Diboronates
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We report a Ni-catalyzed diborylative cyclization of enynes that affords carbo- and heterocycles containing both alkyl- and alkenylboronates. The reaction is fully atom-economical, shows a broad scope, and employs a powerful and inexpensive catalytic Ni-b
- Cabrera-Lobera, Natalia,Quirós, M. Teresa,Brennessel, William W.,Neidig, Michael L.,Bu?uel, Elena,Cárdenas, Diego J.
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supporting information
p. 6552 - 6556
(2019/08/20)
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- Catalyst-Free Annulation of 2-Pyridylacetates and Ynals with Molecular Oxygen: An Access to 3-Acylated Indolizines
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A catalyst and additive-free annulation of 2-pyridylacetates and ynals under molecular oxygen was the first developed, affording 3-acylated indolizines in good to excellent yields. Molecular oxygen was used as the source of the carbonyl oxygen atom in indolizines. This approach was compatible with a wide range of functional groups, and especially it has been successfully extended to unsaturated double bonds and triple bonds, which were difficult to prepare by previous methods in a single step.
- Chen, Zhengwang,Liang, Pei,Ma, Xiaoyue,Luo, Haiqing,Xu, Guohai,Liu, Tanggao,Wen, Xiaowei,Zheng, Jing,Ye, Hui
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supporting information
p. 1630 - 1639
(2019/01/26)
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- Metal-free aminothiation of alkynes: Three-component tandem annulation toward indolizine thiones from 2-alkylpyridines, ynals, and elemental sulfur
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A metal-free three-component annulation reaction for the synthesis of indolizine thiones via tandem C-C/C-N/C-S bond formation was developed. Various 2-alkylpyridines with aromatic ynals and elemental sulfur proceeded smoothly under catalyst-free conditions, and the desired products were obtained in moderate to excellent yields.
- Chen, Zhengwang,Liang, Pei,Xu, Fan,Deng, Zhen,Long, Lipeng,Luo, Guotian,Ye, Min
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supporting information
p. 12639 - 12647
(2019/10/11)
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- A Garratt-Braverman cyclization route towards the synthesis of phenanthridine derivatives and their DNA-binding studies
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Garratt-Braverman cyclization has been employed to synthesize a series of dihydroisofuran fused phenanthridine derivatives. The established protocol proposes a simpler synthetic alternative to have access to these therapeutically relevant cytotoxic scaffo
- Mandal, Arundhoti,Bhattacharya, Prabuddha,Das, Amit K.,Basak, Amit
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p. 1975 - 1987
(2019/02/24)
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- CsF-Mediated in Situ Desilylation of TMS-Alkynes for Sonogashira Reaction
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A practical and mild set of conditions for the Sonogashira reaction utilizing CsF-mediated in situ TMS-alkyne desilylation followed by Sonogashira coupling has been developed for the synthesis of a variety of alkynyl benzenes and heteroarenes in good to excellent yields. This methodology demonstrates excellent functional group tolerance and simple purification, which allows large-scale industrial applications. This one-pot protocol enables a high-yielding Sonogashira coupling with volatile alkynes by avoiding challenging isolation of free alkynes.
- Capani, Joseph S.,Cochran, John E.,Liang, Jianglin
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p. 9378 - 9384
(2019/07/08)
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- Bi(OTf)3 catalyzed synthesis of acyclic β-sulfanyl ketones via a tandem Meyer-Schuster rearrangement/conjugate addition reaction
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A new strategy to prepare acyclic β-carbonyl thioethers from propargyl alcohols and sulfur nucleophiles is reported. The investigation of the reaction substrates scope indicated that primary 3-aryl propargyl alcohols and thiols underwent the transformation smoothly. The reaction probably proceeded a Bi(OTf)3-catalyzed tandem Meyer-Schuster rearrangement of 3-aryl propargyl alcohol, followed by a thiol Michael conjugate addition of thiols to in situ generated α, β-unsaturated ketones. The method was 100% atom economic, high-yielding, and easy to handle, making it a valuable method for the construction of β-carbonyl sulfides.
- Wang, Yuan,Yin, Yan,Zhang, Qinglin,Pan, Wanyong,Guo, Huifeng,Pei, Keke
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supporting information
p. 2030 - 2034
(2019/07/03)
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- Palladium nanoparticles immobilized on cyclodextrin-decorated halloysite nanotubes: Efficient heterogeneous catalyst for promoting copper- and ligand-free Sonogashira reaction in water–ethanol mixture
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Combining the excellent features of halloysite nanoclay and cyclodextrin, a novel hybrid system was designed and synthesized based on covalent attachment of tosylated cyclodextrin to thiosemicarbazide-functionalized halloysite nanoclay and used for the im
- Sadjadi, Samahe
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- Regioselective Synthesis of Indene from 3-Aryl Propargylic gem-Dipivalates Catalyzed by N-Heterocyclic Carbene Gold(I) Complexes
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1-Aryl-3,3-bis(pivaloyloxy)propynes can be converted in good to high yields into either 1,3- or 1,2-bis(pivaloyloxy)indenes, depending on the N-heterocyclic carbene (NHC) gold(I) hexafluoroantimonate catalyst used. Almost exclusive formation of 1,3-di(oxycarbonyl)indene derivatives was achieved with cationic gold complexes containing the embracing N,N′-1,3-bis(9-butylfluorenyl)benzimidazolylidene ligand (nBuFNHC). The regioselective issue of the reaction was rationalized by the specific spatial distribution of the steric bulk in the nBuFNHC ligand. In contrast, only modest selectivities in favor of 1,2-disubstituted indenes were observed with more classical NHC gold complexes, the best selectivity being then obtained with N,N′-1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolylidene gold chloride (SIPrAuCl) as precatalyst. (Figure presented.).
- Hueber, Damien,Teci, Matthieu,Brenner, Eric,Matt, Dominique,Weibel, Jean-Marc,Pale, Patrick,Blanc, Aurélien
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supporting information
p. 2453 - 2459
(2018/05/14)
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- Synthesis and antiviral activity of novel spirocyclic nucleosides
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The synthesis of a number of spirocyclic ribonucleosides containing either a triazolic or azetidinic system is described, along with two analogous phosphonate derivatives of the former. These systems were constructed from the same β-d-psicofuranose starti
- Cobb, Alexander J. A.,Dell'Isola, Antonio,Abdulsattar, Ban O.,McLachlan, Matthew M. W.,Neuman, Benjamin W.,Müller, Christin,Shankland, Kenneth,Al-Mulla, Hawaa M. N.,Binks, Alexander W. D.,Elvidge, Warren
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p. 18363 - 18380
(2018/11/23)
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- Iron-Catalyzed Hydroborylative Cyclization of 1,6-Enynes
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We report first Fe-catalyzed hydroborylative cyclization reaction. The process provides one C?C and one C?B bond in a single operation and shows a wide scope, allowing the formation of carbo- and heterocycles containing a homoallylic boryl unit that can b
- Cabrera-Lobera, Natalia,Rodríguez-Salamanca, Patricia,Nieto-Carmona, Juan C.,Bu?uel, Elena,Cárdenas, Diego J.
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supporting information
p. 784 - 788
(2017/11/29)
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- Iron-Catalyzed Coupling of Propargyl Bromides and Alkyl Grignard Reagents
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An iron-catalyzed Kumada-type cross-coupling reaction of propargyl halides with alkylmagnesium reagents is described. The reaction is fast, takes place in smooth conditions, tolerates several functional groups that would be able to react with the Grignard reagent, and may afford either allene or propargyl coupling derivatives. Factors involved in the observed regioselectivity have been studied.
- Domingo-Legarda, Pablo,Soler-Yanes, Rita,Quirós-López, M. Teresa,Bu?uel, Elena,Cárdenas, Diego J.
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supporting information
p. 4900 - 4904
(2018/09/10)
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- Nickel(II)-Catalyzed Asymmetric Propargyl [2,3] Wittig Rearrangement of Oxindole Derivatives: A Chiral Amplification Effect
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A highly enantioselective [2,3] Wittig rearrangement of oxindole derivatives was realized by using a chiral N,N′-dioxide/NiII complex as the catalyst under mild reaction conditions. A strong chiral amplification effect was observed, and allowed access to chiral 3-hydroxy 3-substituted oxindoles bearing allenyl groups in high yields and enantioselectivities (up to 92 % ee) by using a ligand with only 15 % ee. A reasonable explanation was given based on the experimental investigations and X-ray crystal structures of enantiomerically pure and racemic catalysts. Moreover, the first catalytic kinetic resolution of racemic oxindole derivatives by a [2,3] Wittig rearrangement was realized with high efficiency and stereoselectivity.
- Xu, Xi,Zhang, Jianlin,Dong, Shunxi,Lin, Lili,Lin, Xiaobin,Liu, Xiaohua,Feng, Xiaoming
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supporting information
p. 8734 - 8738
(2018/07/14)
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- Harnessing Nucleophilicity of Allenol Ester with p-Quinone Methides via Gold Catalysis: Application to the Synthesis of Diarylmethine-Substituted Enones
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A gold(I)-catalyzed protocol for intermolecular 1,6-conjugate addition of nucleophilic allenol ester generated in situ through [3,3]-sigmatropic rearrangement with p-quinone methides (p-QMs) has been developed. The gold catalyst plays a dual role by the acid-triggered activation of alkynes and at the same time as a Lewis acid for activation of p-QMs toward nucleophilic attack. This method enables rapid access to a wide range of densely functionalized diarylmethine-substituted enones, a Morita-Baylis-Hillman (MBH) product with high selectivity, excellent yields, and broad substrate scope.
- Sharma, Brijesh M.,Rathod, Jayant,Gonnade, Rajesh G.,Kumar, Pradeep
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p. 9353 - 9363
(2018/06/29)
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- Palladium nanoparticles immobilized on sepiolite–cyclodextrin nanosponge hybrid: Efficient heterogeneous catalyst for ligand- and copper-free C─C coupling reactions
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A novel hybrid system composed of sepiolite clay and cyclodextrin nanosponge (CDNS) was prepared via reaction of Cl-functionalized sepiolite with amine-functionalized CDNS. CDNS–sepiolite was then applied for immobilization of Pd(0) nanoparticles. The resulting hybrid system, Pd@CDNS-sepiolite, was characterized using various techniques and successfully used as an efficient and heterogeneous catalyst for ligand- and copper-free Sonogashira and Heck coupling reactions under mild reaction conditions. Recycling experiments confirmed that Pd@CDNS-sepiolite was recyclable and could be used for several consecutive reaction runs with slight Pd leaching and loss of catalytic activity.
- Sadjadi, Samahe,Heravi, Majid M.,Raja, Maryam,Kahangi, Fatemeh Ghoreyshi
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- Stereoselective Synthesis of Exocyclic Tetrasubstituted Vinyl Halides via Ru-Catalyzed Halotropic Cycloisomerization of 1,6-Haloenynes
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Herein, a ruthenium-catalyzed cycloisomerization that transforms 1,6-haloenynes into 5-membered carbo- and heterocycles that bear exocyclic, stereodefined, tetrasubstituted vinyl halides is reported. The reaction is insensitive to air and water, tolerates a variety of functional groups, and proceeds with good to excellent stereoselectivity and yield.
- Trost, Barry M.,Kalnmals, Christopher A.
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supporting information
p. 2346 - 2349
(2017/05/12)
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- Magnetic nanoparticle-supported tetrazole-functionalized palladium catalyst: synthesis, DFT study and application for Sonogashira and Heck cross-coupling reactions
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Abstract: A novel magnetic catalyst-immobilized nano-palladium was efficiently prepared via a (2?+?3) cycloaddition pathway and characterized with different analyses, including FT-IR, FE-SEM, EDS, XRD, TEM and VSM methods. Also, topological and NBO analysis of a simple model of the catalyst with the M06/6-311?g(d,p)-LANL2DZ model chemistry have been introduced. In addition, the catalytic pursuit of this novel magnetic nanocatalyst was successfully evaluated in Sonogashira and Heck cross-coupling reactions. Furthermore, the catalyst could be easily separated by a conventional method using a permanent magnet and reused repeatedly in the model reaction without noteworthy loss of its catalytic activity.
- Elhampour, Ali,Nemati, Firouzeh,Nahzomi, Hossein Taherpour,Mohagheghi, Vahid
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p. 6737 - 6761
(2017/10/06)
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- Two-Step Synthesis of (Z)-3-Aryl-5-(arylmethylidene)butenolides by an Ivanov Reaction/Silver(I)-Catalyzed Lactonization/In Situ Dehydration Sequence
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A stereoselective synthesis of the title compounds was developed. Hexane- and amine-free THF solutions of α-lithiated lithium arylacetates ('arylacetic acid dianions') were aldol-added to 3-arylpropynals. This gave 2,5-diaryl-3-hydroxypent-4-ynoic acids with up to a 72:28 preference for the anti-diastereomer (27 examples + 1 exception). When treated with Ag2CO3 (1-20 mol%) in DMF at room temperature for 2.5 days, the respective mixtures underwent regio- and stereoselective lactonizations followed by an in situ dehydration. Thereby 3-aryl-5-(arylmethylidene)butenolides were obtained with a Z-configuration of the oxygenated C=C bond. Their overall yields ranged from 46% to 83% (1 exception: 28%). Three 3-aryl-5-(arylmethylidene)butenolides contained a C-Br and/or a C-I bond. They allowed a subsequent Pd-catalyzed C-C coupling, which furnished follow-up butenolides.
- Hermann, David,Arican, Deniz,Brückner, Reinhard
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p. 326 - 352
(2016/12/24)
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- Cobalt-catalyzed (Z)-selective semihydrogenation of alkynes with molecular hydrogen
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Cobalt-catalyzed highly (Z)-selective semihydrogenation of alkynes using molecular H2 was developed using commercially available and cheap cobalt precursors. A variety of (Z)-alkenes were obtained in moderate to excellent selectivities [(Z)-alkene/(E)-alkene/alkane ratio up to >99 : 1 : 1] and it was found that the readily available ethylenediamine ligand is crucial in determining the selectivity.
- Chen, Caiyou,Huang, Yi,Zhang, Zongpeng,Dong, Xiu-Qin,Zhang, Xumu
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supporting information
p. 4612 - 4615
(2017/04/28)
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- Heat Versus Basic Conditions: Intramolecular Dehydro-Diels-Alder Reaction of 1-Indolyl-1,6-heptadiynes for the Selective Synthesis of Substituted Carbazoles
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The intramolecular dehydro-Diels-Alder reaction of 1-indolyl-1,6-heptadiynes proceeds smoothly under rather mild heating conditions to give substituted carbazoles in moderate to good yields. The reaction of 7-aryl-1-indolyl-1,6-heptadiynes under heating gives the corresponding carbazoles chemoselectively in high yields, whereas the reaction under basic conditions gives naphthalenes as major products.
- Kudoh, Takayuki,Fujisawa, Syo,Kitamura, Megumi,Sakakura, Akira
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supporting information
p. 2189 - 2193
(2017/09/26)
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- Redox-Neutral Arylations of Vinyl Cation Intermediates
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Herein we present a new unified concept for C?C bond formation under redox-neutral conditions. Our strategy hinges upon interception of a vinyl cation with a sulfoxide resulting in simultaneous C–C and C?O bond formation and arylation. A range of structurally diverse vinyl cations are generated in situ in the presence of a sulfoxide, resulting in hydrative arylation, direct arylation of enol triflates and interrupted Meyer–Schuster rearrangement. Mechanistic investigations showcase the crucial role played by the fleeting vinyl cation intermediate and structural features that lead to its stabilization. Applications of the reaction products to synthesis are also presented. (Figure presented.).
- Kaiser, Daniel,Veiros, Luis F.,Maulide, Nuno
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supporting information
p. 64 - 77
(2017/01/14)
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- Sodium Phenoxide Mediated Hydroxymethylation of Alkynylsilanes with N-[(Trimethylsiloxy)methyl]phthalimide
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The hydroxymethylation of alkynylsilanes with formaldehyde generated in situ from N-[(trimethylsiloxy)methyl]phthalimide proceeds in the presence of a stoichiometric amount of NaOPh. The reaction occurs at room temperature by using an operationally simple one-step procedure. A variety of alkynylsilanes possessing electron-donating, electron-withdrawing, and halogen groups (including heteroaryl-substituted alkynylsilanes) provide hydroxymethylated products.
- Asano, Narumi,Sasaki, Keita,Chataigner, Isabelle,Shigeno, Masanori,Kondo, Yoshinori
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supporting information
p. 6926 - 6930
(2017/12/26)
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- Fe(OTf)3-catalyzed tandem Meyer-Schuster rearrangement/intermolecular hydroamination of 3-aryl propargyl alcohols for the synthesis of acyclic β-Aminoketones
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Fe(OTf)3-catalyzed synthesis of acyclic β-aminoketones from 3-aryl propargyl alcohols and nitrogen nucleophiles were investigated. Results showed that propargyl alcohols without bulky groups α to the hydroxyl group underwent the transformation smoothly. Sulphonamides exhibited the higher reactivity than amides as the nitrogen nucleophiles and the transformation of acyclic β-aminoketones were finished in shorter reaction time and higher yields. Finally, racemic fluoxetine was efficiently accessed with the present reaction as the first step. This novel synthesis of acyclic β-aminoketones probable proceeded a Fe(OTf)3-catalyzed Meyer-Schuster rearrangement of 3-aryl propargyl alcohols, followed by a intermolecular hydroamination between nitrogen nucleophiles and α, β-unsaturated ketones.
- Tao, Ruiheng,Yin, Yan,Duan, Yongbin,Sun, Yuxing,Sun, Yue,Cheng, Fengkai,Pan, Jinpeng,Lu, Cheng,Wang, Yuan
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p. 1762 - 1768
(2017/03/08)
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- Chemoproteomics-Enabled Discovery of a Potent and Selective Inhibitor of the DNA Repair Protein MGMT
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We present a novel chemical scaffold for cysteine-reactive covalent inhibitors. Chloromethyl triazoles (CMTs) are readily accessed in only two chemical steps, thus enabling the rapid optimization of the pharmacological properties of these inhibitors. We d
- Wang, Chao,Abegg, Daniel,Hoch, Dominic G.,Adibekian, Alexander
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supporting information
p. 2911 - 2915
(2016/02/27)
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- 3-ARYL PROPIOLONITRILE COMPOUNDS FOR THIOL LABELING
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The present invention relates to a process for labeling compounds comprising thiol moieties with 3-arylpropiolonitrile compounds, to 3-arylpropiolonitrile compounds substituted with tag moieties and to specific 3-arylpropiolonitrile linkers.
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Paragraph 0168; 0174; 0179-0180
(2016/06/13)
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- Catalytic Enantioselective Synthesis of Amino Skipped Diynes
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The Cu-catalyzed synthesis of nonracemic 3-amino skipped diynes via an enantiodetermining C-C bond formation is described using StackPhos as ligand. Despite challenging issues of reactivity and stereoselectivity inherent to these chiral skipped diynes, the reaction tolerates an extremely broad substrate scope with respect to all components and provides the title compounds in excellent enantiomeric excess. The alkyne moieties are demonstrated here to be useful synthetic handles, and 3-amino skipped diynes are convenient building blocks for enantioselective synthesis.
- Paioti, Paulo H. S.,Abboud, Khalil A.,Aponick, Aaron
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supporting information
p. 2150 - 2153
(2016/03/05)
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- Facile synthesis of substituted 3-aminofurans through a tandem reaction of N-sulfonyl-1,2,3-triazoles with propargyl alcohols
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A relay catalysis strategy for substituted 3-aminofurans synthesis has been developed. This transformation involves a tandem reaction sequence through aza-vinyl-rhodium(ii) carbene O-H bond insertion, thermal propargyl-Claisen rearrangement and gold(i)-catalyzed intramolecular cyclization. More importantly, the current strategy employs simple feedstocks as starting materials, providing substituted 3-aminofurans in a highly efficient manner.
- Cheng, Xing,Yu, Yinghua,Mao, Zhifeng,Chen, Jianxin,Huang, Xueliang
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supporting information
p. 3878 - 3882
(2016/06/01)
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- Enantioselective Carbene Cascade: An Effective Approach to Cyclopentadienes and Applications in Diels–Alder Reactions
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An asymmetric carbene cascade reaction, which proceeds through carbene/alkyne metathesis and formal (3+2) cycloaddition and converts alkynyl-tethered enol diazoacetates to chiral bicyclic cyclopentadienes, is presented; and no catalytic asymmetric version of these carbene cascade transformations has been disclosed so far. The proton signals of the cyclopropene intermediates are observed in the mechanism study, which clearly demonstrate the reaction pathways. In addition, these products are intercepted via Diels–Alder reactions to provide bridged polycyclic structures in high yields and enantioselectivities. (Figure presented.).
- Wang, Xiangbo,Zhou, Yunfei,Qiu, Lihua,Yao, Ruwei,Zheng, Yang,Zhang, Cheng,Bao, Xiaoguang,Xu, Xinfang
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supporting information
p. 1571 - 1576
(2016/10/13)
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- Squaramide catalyzed enantioselective iodolactonization of allenoic acids
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An asymmetric iodolactonization reaction of allenoic acids has been extensively studied. Eight different chiral squaramides were prepared in a straightforward manner and investigated as organocatalysts. The reaction protocol is operationally simple to exe
- Kristianslund, Renate,Aursnes, Marius,Tungen, J?rn Eivind,Hansen, Trond Vidar
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supporting information
p. 5232 - 5236
(2016/11/13)
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- Expedient synthesis of new cinnoline diones by Ru-catalyzed regioselective unexpected deoxygenation-oxidative annulation of propargyl alcohols with phthalazinones and pyridazinones
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Ruthenium-catalyzed simple, cascade and one-pot synthesis of cinnoline-fused diones has been carried out by the C-H activation of phthalazinones/pyridazinones accomplished by the unusual deoxygenation of propargyl alcohols. The bond selectivity is accredited to the traceless directing nature of the hydroxyl group of propargyl alcohol. A sequential C-H activation, insertion and deoxy-oxidative annulation has been proposed based on the preliminary mechanistic study.
- Rajkumar, Subramani,Antony Savarimuthu,Senthil Kumaran, Rajendran,Nagaraja,Gandhi, Thirumanavelan
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supporting information
p. 2509 - 2512
(2016/02/12)
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- Gold(I)-Catalyzed Angle Strain Controlled Strategy to Furopyran Derivatives from Propargyl Vinyl Ethers: Insight into the Regioselectivity of Cycloisomerization
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A unique strategy for the regiospecific synthesis of bicyclic furopyran derivatives has been developed via a gold(I)-catalyzed propargyl-Claisen rearrangement/6-endo-trig cyclization of propargyl vinyl ethers. The introduction of angle strain into the substrates significantly altered the reaction's regioselectivity. Insight into the regioselectivity of the cycloisomerization was obtained with density functional theory calculations. (Chemical Equation).
- Jin, Shengfei,Jiang, Chongguo,Peng, Xiaoshi,Shan, Chunhui,Cui, Shanshan,Niu, Yuanyuan,Liu, Yang,Lan, Yu,Liu, Yongxiang,Cheng, Maosheng
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supporting information
p. 680 - 683
(2016/03/01)
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- A gold(i)-catalyzed substituent-controlled cycloisomerization of propargyl vinyl ethers to multi-substituted furofuran and furopyran derivatives
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A gold(i)-catalyzed substituent-controlled strategy for the stereoselective synthesis of bicyclic furan and pyran derivatives has been developed. The mechanisms of the reactions have been studied thoroughly by deuterium labelling experiments. The applications of the methodologies were demonstrated by evaluating the preliminary anti-fungal activity of the synthetic compounds.
- Liu, Yongxiang,Jin, Shengfei,Wang, Yanshi,Cui, Shanshan,Peng, Xiaoshi,Niu, Yuanyuan,Du, Chuan,Cheng, Maosheng
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supporting information
p. 6233 - 6236
(2016/05/24)
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- Ligand-Controlled Regioselective Copper-Catalyzed Trifluoromethylation To Generate (Trifluoromethyl)allenes
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(Chemical Equation Presented) "Cu-CF3" species have been used historically for a broad spectrum of nucleophilic trifluoromethylation reactions. Although recent advancements have employed ligands to stabilize and harness the reactivity of this key organometallic intermediate, the ability of a ligand to differentiate a regiochemical outcome of a Cu-CF3-mediated or -catalyzed reaction has not been previously reported. Herein, we report the first example of a Cu-catalyzed trifluoromethylation reaction in which a ligand controls the regiochemical outcome. More specifically, we demonstrate the ability of bipyridyl-derived ligands to control the regioselectivity of the Cu-catalyzed nucleophilic trifluoromethylation reactions of propargyl electrophiles to generate (trifluoromethyl)allenes. This method provides a variety of di-, tri-, and tetrasubstituted (trifluoromethyl)allenes, which can be further modified to generate complex fluorinated substructures.
- Ambler, Brett R.,Peddi, Santosh,Altman, Ryan A.
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supporting information
p. 2506 - 2509
(2015/05/27)
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- Facile and surfactant-free synthesis of Pd nanoparticles by the extract of the fruits of Piper longum and their catalytic performance for the Sonogashira coupling reaction in water under ligand- and copper-free conditions
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This work reports a facile synthesis of palladium nanoparticles (Pd NPs) by the extract of the fruits of Piper longum without any stabilizer or surfactant. The Pd NPs were found to be effective catalysts for the ligand-, amine- and copper-free Sonogashira
- Nasrollahzadeh, Mahmoud,Mohammad Sajadi,Maham, Mehdi,Ehsani, Ali
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p. 2562 - 2567
(2015/02/05)
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