- Characterization of heterogeneous aryl-Pd(ii)-oxo clusters as active species for C-H arylation
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C-H arylation with heterogeneous palladium was investigated. The surface oxidation of Pd nanoparticles with a hypervalent iodine reagent, [Ph2I]BF4, resulted in the generation of Pd(ii)-aryl-oxo clusters, which were characterized as the crucial intermediate.
- Shin, Taeil,Kim, Minjun,Jung, Younjae,Cho, Sung June,Kim, Hyunwoo,Song, Hyunjoon
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supporting information
p. 14404 - 14407
(2020/12/01)
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- Photoredox catalysis using infrared light via triplet fusion upconversion
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Recent advances in photoredox catalysis have made it possible to achieve various challenging synthetic transformations, polymerizations and surface modifications1–3. All of these reactions require ultraviolet- or visible-light stimuli; however,
- Ravetz, Benjamin D.,Pun, Andrew B.,Churchill, Emily M.,Congreve, Daniel N.,Rovis, Tomislav,Campos, Luis M.
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p. 343 - 346
(2019/01/26)
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- TRIPLET FUSION UPCONVERSION FOR INFRARED-SENSITIZED PHOTOREDOX CHEMISTRY
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Various exemplary photoreactions can be provided, including reactions generally based on triplet-triplet annihilation upconversion. Representative photosensitizers include PdPc(OBu)8 and PtTPTNP. Representative annihilators include FDPP and TTBP. Such exe
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Paragraph 0125
(2019/09/20)
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- Heteroleptic Copper(I)-Based Complexes for Photocatalysis: Combinatorial Assembly, Discovery, and Optimization
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A library of 50 copper-based complexes derived from bisphosphines and diamines was prepared and evaluated in three mechanistically distinct photocatalytic reactions. In all cases, a copper-based catalyst was identified to afford high yields, where new heteroleptic complexes derived from the bisphosphine BINAP displayed high efficiency across all reaction types. Importantly, the evaluation of the library of copper complexes revealed that even when photophysical data is available, it is not always possible to predict which catalyst structure will be efficient or inefficient in a given process, emphasizing the advantages for catalyst structures with high modularity and structural variability.
- Minozzi, Clémentine,Caron, Antoine,Grenier-Petel, Jean-Christophe,Santandrea, Jeffrey,Collins, Shawn K.
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supporting information
p. 5477 - 5481
(2018/05/01)
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- BICYCLIC INHIBITORS OF PAD4
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The present invention provides compounds useful as inhibitors of PAD4, compositions thereof, and methods of treating PAD4-related disorders.
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Paragraph 00155
(2017/07/06)
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- HETEROARYL INHIBITORS OF PAD4
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The present invention provides compounds useful as inhibitors of PAD4, compositions thereof, and methods of treating PAD4-related disorders.
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Paragraph 00119-00121
(2017/09/15)
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- Palladium-catalyzed regioselective C-2 arylation of 7-azaindoles, indoles, and pyrroles with arenes
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A palladium-catalyzed regioselective C-2 arylation of 7-azaindoles, indoles, and pyrroles with arenes has been developed. This study unveils that a critical substrate dependent acid concentration is essential for achieving exclusive C-2 selectivity as wel
- Laha, Joydev K.,Bhimpuria, Rohan A.,Prajapati, Dilip V.,Dayal, Neetu,Sharma, Shubhra
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supporting information
p. 4329 - 4332
(2016/03/22)
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- A porous metal-organic cage constructed from dirhodium paddle-wheels: Synthesis, structure and catalysis
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Self-assembly of dirhodium(ii) tetraacetate (Rh2(OAc)4) with a dicarboxylic acid 3,3′-(1,3-phenylenebis(ethyne-2,1-diyl))dibenzoic acid (H2pbeddb) gives rise to a metal-organic cage (MOC) containing Rh-Rh bonds with the formula of [Rh4(pbeddb)4(H2O)2(DMAC)2] (MOC-Rh-1). Single-crystal X-ray diffraction analysis reveals that MOC-Rh-1 shows a lantern-type cage structure, in which a pair of Rh2(CO2)4 paddlewheels is linked by four diacid ligands. The dimensions of the inner cavity of MOC-Rh-1 are 9.5 × 14.8 ?2 (atom-to-atom distances across opposite metal and phenyl groups of pbeddb2-). In the solid phase, the cages are aligned by π-π stacking to form one-dimensional channels (9.5 × 11.1 ?2) through cage windows. Therefore, the crystalline samples of MOC-Rh-1 are porous with the inner and outer cavities of the cages accessible under the heterogeneous condition. MOC-Rh-1 has been fully characterized by EA, TGA, PXRD, IR, UV-vis and XPS measurements. The catalytic tests disclose that activated MOC-Rh-1 is effective in the intramolecular C-H amination of vinyl, dienyl and biaryl azides, leading to the formation of indoles, pyrroles and carbazoles, respectively, and the porous catalyst can be recycled easily and used for at least nine runs without significant loss of activity. In the nine runs, the conversions were in the range of 93-99%, whereas in the tenth run, the conversion was reduced to 78%.
- Chen, Lianfen,Yang, Tao,Cui, Hao,Cai, Tao,Zhang, Li,Su, Cheng-Yong
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supporting information
p. 20201 - 20209
(2015/10/19)
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- Visible-light sensitization of vinyl azides by transition-metal photocatalysis
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Irradiation of vinyl and aryl azides with visible light in the presence of Ru photocatalysts results in the formation of reactive nitrenes, which can undergo a variety of C-N bond-forming reactions. The ability to use low-energy visible light instead of UV in the photochemical activation of azides avoids competitive photodecomposition processes that have long been a significant limitation on the synthetic use of these reactions. Rock and pyrrole: Irradiation of vinyl and aryl azides with visible light in the presence of Ru photocatalysts results in the formation of reactive nitrenes, which can undergo a variety of C-N bond-forming reactions. The ability to use low-energy visible light instead of UV in the photochemical activation of azides (see picture) avoids competitive photodecomposition processes. Copyright
- Farney, Elliot P.,Yoon, Tehshik P.
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supporting information
p. 793 - 797
(2014/01/23)
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- Phenyl α-bromovinyl sulfone in cycloadditions with azomethine ylides: An unexpected facile aromatization of the cycloadducts into pyrroles
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Phenyl α-bromovinyl sulfone reacts with glycine ester Schiff bases regioselectively in the presence of catalytic amounts of AgOAc and DBU yielding polysubstituted pyrrolidine cycloadducts. Utilization of excess DBU induces subsequent facile aromatization of the cycloadducts and affords 5-arylpyrrole-2-carboxylic acid esters in 39-85% yields in a single step.
- Kudryavtsev, Konstantin V.,Ivantcova, Polina M.,Churakov, Andrei V.,Vasin, Victor A.
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experimental part
p. 4300 - 4303
(2012/09/22)
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- Continuous flow thermolysis of azidoacrylates for the synthesis of heterocycles and pharmaceutical intermediates
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An efficient, safe and scalable procedure for the continuous flow thermolysis of azidoacrylates to yield indoles has been developed and was applied to the synthesis of related heterocycles. The scalability of the process was demonstrated in the continuous flow synthesis of a precursor to the DAAO inhibitor 4H-furo[3,2-b]pyrrole-5-carboxylic acid.
- O'Brien, Alexander G.,Levesque, Francois,Seeberger, Peter H.
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supporting information; experimental part
p. 2688 - 2690
(2011/04/25)
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- Pyrrole and oligopyrrole synthesis by 1,3-dipolar cycloaddition of azomethine ylides with sulfonyl dipolarophiles
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A procedure for the synthesis of functionalized, substituted pyrroles by 1,3-dipolar cycloaddition of azomethine ylides has been developed. This protocol is based on the metal-catalyzed cycloaddition of α-iminoesters with sulfonyl dipolarophiles, followed by the base-promoted elimination of the sulfonyl groups. A wide variety of 2,5-disubstituted and 2,3,5- and 2,4,5trisubstituted pyrroles have been prepared in satisfactory yields from 1,2bis(sulfonyl ethylene), ss-sulfonylenones, and ss- sulfonylacrylates. This method can be applied in an iterative and straightforward manner to the construction of oligopyrroles, from bipyrroles to pentapyrroles. Iterative [n+1] and [n+2] approaches have been devised, the latter involves double 1,3-dipolar cycloaddition from pyrrolylbased bis(iminoesters).
- Robles-Machin, Rocio,Lopez-Perez, Ana,Gonzalez-Esguevillas, Maria,Adrio, Javier,Carretero, Juan Carlos
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supporting information; experimental part
p. 9864 - 9873
(2010/11/16)
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- Phosphine-free palladium-catalyzed C-H bond arylation of free (N-H)-indoles and pyrroles
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(Chemical Equation Presented) This paper describes a phosphine-free palladium-catalyzed method for direct C-arylation of free (N-H)-indoles and pyrroles with iodo- and bromoarene donors. Employing commercially available materials, this new and operationally simple procedure provides a rapid entry to a wide range of C-arylated (N-H)-indoles including derivatives of tryptamine. In the course of this study, a profound halide effect was uncovered, affecting both the efficiency and regioselectivity of indole arylation.
- Wang, Xiang,Gribkov, Denis V.,Sames, Dalibor
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p. 1476 - 1479
(2007/10/03)
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- Oligopyrrole synthesis by 1,3-dipolar cycloaddition of azomethine ylides with bissulfonyl ethylenes
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(Chemical Equation Presented) One by one or two by two: In a general approach to the iterative construction of oligopyrroles, the cycloaddition of azomethine ylides derived from pyrrolyl α-iminoesters with 1,2-bis(phenylsulfonyl)-ethylene is followed by the elimination of the sulfonyl groups in situ under basic conditions. This strategy is amenable to the introduction of one or two pyrrole units in each iterative cycle.
- Lopez-Perez, Ana,Robles-Machin, Rocio,Adrio, Javier,Carretero, Juan Carlos
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p. 9261 - 9264
(2008/12/22)
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- Transition metal-catalyzed synthesis of pyrroles from dienyl azides
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(Chemical Equation Presented) A range of 2,5-disubstituted and 2,4,5-trisubstituted pyrroles can be synthesized from dienyl azides at room temperature using catalytic amounts of Znl2 or Rh2(O 2CC3F7)4.
- Dong, Huijun,Shen, Meihua,Redford, Joanne E.,Stokes, Benjamin J.,Pumphrey, Ashley L.,Driver, Tom G.
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p. 5191 - 5194
(2008/09/17)
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- The regioselective synthesis of aryl pyrroles
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Pyrrole is a unique aromatic molecule as it can readily undergo substitution at all five positions but obtaining the desired regioisomer can prove difficult to control. We now report our results on the regioselective arylation of pyrrole, utilizing select
- Smith, Jason A.,Ng, Sarah,White, Jonathon
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p. 2477 - 2482
(2008/03/11)
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- Transition metal catalyzed ring opening reactions of 2-phenyl-3-vinyl substituted 2H-azirines
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Treatment of 2-phenyl-3-vinyl-substituted 2H-azirines with Grubbs' catalyst induces a clean rearrangement and affords products derived from carbon-nitrogen bond cleavage of the 2H-azirine ring. However, when the reaction was carried out using Wilkinson's catalyst in an alcoholic solvent, the only product obtained in high yield corresponded to an α,β-unsaturated oxime.
- Padwa, Albert,Stengel, Thomas
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p. 5991 - 5993
(2007/10/03)
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- The synthesis of 5-substituted proline derivatives and of 5-substituted pyrrole-2-carboxylates by 5-endo cyclisations featuring a method for effectively favouring these with respect to 5-exo cyclisations
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Overall 5-endo cyclisations of the C-allylic glycine sulfonamides 5 lead to usually excellent yields of the 2,5-cis- or 2,5-trans-pyrrolidine-2-carboxylates 11 and 12 respectively, depending upon whether base is absent or present. While reductions to the corresponding pyrrolidine-2-methanols 13 proved efficient, subsequent eliminations of the elements of hydrogen iodide gave mixtures of products 14-16. Suitably positioned hydroxy groups compete successfully with the sulfonamide via a 5-exo cyclisation mode. However, when such a substrate contains a furan ring attached to the alkene function (21), then cyclisation does occur at the sulfonamide, presumably by participation of the furan oxygen, to give an iodopyrrolidine-2-methanol 13a. Finally, base-induced elimination of both hydrogen iodide and toluene-p-sulfinic acid from the initial iodopyrrolidines 11 and 12 leads to 5-substituted pyrrole-2-carboxylates 26. Overall, this sequence is complementary to the Kenner pyrrole synthesis.
- Knight,Redfern,Gilmore
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p. 2874 - 2883
(2007/10/03)
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- A new approach to 5-substituted prolines and 2-pyrrolecarboxylates
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Iodocyclisations of the allylic glycinates 7 lead either to the trans- or cis-2,5-disubstituted proline derivatives 8 or 9, depending on the reaction conditions; subsequent treatment of these with DBU in DMF gives the 2-pyrrolecarboxylates 10 and 13 in excellent yields by a double elimination of hydrogen iodide and toluenesulfinic acid.
- Knight, David W.,Redfern, Adele L.,Gilmore, Jeremy
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p. 731 - 732
(2007/10/03)
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- Double diastereoselectivite de la cycloaddition dipolaire-1,3 d'ylures d'azomethine cycliques substitues
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Seven derivatives of methyl 5-phenyl-3,4-dihydro-2H-pyrrole-2-carboxylates 1 were synthesized.These compounds are precursors of pentagonal cyclic azomethine ylides, the two sides of which are diastereotopic.The 1,3-dipolar species react with N-methyl and
- Lakhlifi, Tahar,Sedqui, Ahmed,Fathi, Toufik,Laude, Bernard,Robert, Jean-Francois
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p. 1417 - 1423
(2007/10/02)
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