- Copper-Catalyzed Modular Access to N-Fused Polycyclic Indoles and 5-Aroyl-pyrrol-2-ones via Intramolecular N—H/C—H Annulation with Alkynes: Scope and Mechanism Probes
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Copper-catalyzed intramolecular N—H/C—H annulation with alkynes has been developed. A variety of densely functionalized heterocycles, such as pyrrolo[1,2-a]indoles, indolo[1,2-c]quinazolin-2-ones, oxazolo[3,4-a]indoles, and imidazo[1,5-a]indoles, were synthesized in an atom- and step-economical manner, owing to the high modularized feature of aniline moiety, the linker moiety, as well as the alkyne moiety. By simply changing the oxidant from di-tert-butyl peroxide (DTBP) to 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), the reaction could readily be transformed to the aminooxygenation pathway, which grabs one oxygen atom from the TEMPO to generate 5-aroyl-pyrrol-2-ones. Mechanistic experiments indicate that vinyl radical is involved in this reaction and an amidyl-radical-initiated radical cascade might be responsible for this transformation.
- Liu, Yan-Hua,Song, Hong,Zhang, Chi,Liu, Yue-Jin,Shi, Bing-Feng
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supporting information
p. 1545 - 1552
(2020/09/09)
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- Enantioselective Construction of Tertiary Fluoride Stereocenters by Organocatalytic Fluorocyclization
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1,1-Disubstituted styrenes with internal oxygen and nitrogen nucleophiles undergo oxidative fluorocyclization reactions with in situ generated chiral iodine(III)-catalysts. The resulting fluorinated tetrahydrofurans and pyrrolidines contain a tertiary carbon-fluorine stereocenter. Application of a new 1-naphthyllactic acid-based iodine(III)-catalyst allows the control of tertiary carbon-fluorine stereocenters with up to 96% ee. Density functional theory calculations are performed to investigate the details of the mechanism and the factors governing the stereoselectivity of the reaction.
- Biosca, Maria,Eriksson, Lars,Hedberg, Martin,Himo, Fahmi,Lübcke, Marvin,Szabó, Kálmán J.,Wang, Qiang
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supporting information
p. 20048 - 20057
(2020/11/27)
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- Synthesis and Utility of 2,2-Dimethyl-2 H-pyrans: Dienes for Sequential Diels-Alder/Retro-Diels-Alder Reactions
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The practical use of 2,2-dimethyl-2H-pyrans as electron-rich dienes in sequential Diels-Alder/retro-Diels-Alder (DA/rDA) domino processes to generate aromatic platforms has been demonstrated. Different polysubstituted alkyl 2-naphthoates have been synthesized by the DA/rDA reaction of benzynes and 2,2-dimethyl-2H-pyrans. The use of other activated alkynes allows the access of substituted alkyl benzoate derivatives.
- Tejedor, David,Díaz-Díaz, Abián,Diana-Rivero, Raquel,Delgado-Hernández, Samuel,García-Tellado, Fernando
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supporting information
p. 7987 - 7992
(2019/01/04)
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- CYCLOPROPANECARBOXAMIDE MODULATORS OF CYSTIC FIBROSIS TRANSMEMBRANE CONDUCTANCE REGULATOR
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The present invention relates to new cyclopropanecarboxamide modulators of cystic fibrosis transmembrane conductance regulator proteins, pharmaceutical compositions thereof, and methods of use thereof.
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Paragraph 00164
(2016/08/03)
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- Efficient synthesis and antibacterial activities of some novel 1,2,3-triazoles prepared from propargylic alcohols and benzyl azides
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A simple and effective procedure for regioselective preparation of 1,2,3-triazoles from benzyl azides and propargylic alcohols is described using CuSO4·5H2O and sodium ascorbate. To screen the antibacterial activity of some newly synthesized triazole derivatives, minimum inhibitory concentration of 3d and 3k was evaluated against gram positive Staphylococcus aureus and Bacillus subtilis and gram negative Escherichia coli and Pseudomonas aeruginosa.
- Hosseinzadeh, Rahman,Abolfazli, Mohammadreza Khadem,Mohseni, Mojtaba,Mohadjerani, Maryam,Lasemi, Zahra
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p. 1298 - 1305
(2015/04/27)
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- KINASE INHIBITORS
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There are provided compounds of formula (I), (Formula (I)) wherein R1 to R5, X1, X2, Ar, L, E, A, A1, G and G1 have meanings given in the description, which compounds have antiinflammatory activity (e.g. through inhibition of one or more of members of: the family of p38 mitogen-activated protein kinase enzymes; Syk kinase; and members of the Src family of tyrosine kinases) and have use in therapy, including in pharmaceutical combinations, especially in the treatment of inflammatory diseases, including inflammatory diseases of the lung, eye and intestines.
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Page/Page column 45-46
(2014/03/25)
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- Cobalt-catalyzed carboxylation of propargyl acetates with carbon dioxide
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The cobalt-catalyzed carboxylation of propargyl acetates with CO2 (1 atm) is described. The reaction proceeds at room temperature in the presence of Mn powder as a reducing reagent. Various propargyl acetates are converted to the corresponding carboxylic acids in good to high yields.
- Nogi, Keisuke,Fujihara, Tetsuaki,Terao, Jun,Tsuji, Yasushi
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supporting information
p. 13052 - 13055
(2015/02/19)
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- Synthesis of α-arylated allylsilanes through palladium-catalyzed γ-selective allyl-aryl coupling
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(Equation Presented). A palladium-catalyzed γ-selective allyl-aryl coupling between γ-silylated allylic esters and arylboronic acids produced α-arylated allylsilanes with E-alkene geometry. The reaction tolerated various functional groups in both the arylboronic acids and the allylic esters and afforded functionalized allylsilanes. The reaction of optically active allylic esters took place with excellent α-to-γ chirality transfer with syn stereochemistry to give chiral allylsilanes.
- Li, Dong,Tanaka, Tatsunori,Ohmiya, Hirohisa,Sawamura, Masaya
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supporting information; experimental part
p. 3344 - 3347
(2010/11/03)
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- A convenient method for the aromatic amino-claisen rearrangement of N-(1,1-disubstituted-allyl)anilines
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N-(1,1-Disubstituted-allyl)anilines are rearranged cleanly and in high yield to 2-(3,3-disubstituted-allyl)anilines using a catalytic amount of p-toluenesulfonic acid in acetonitrile/water (10:1).
- Cooper,Lucas,Taylor,Ward,Williamson
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p. 621 - 625
(2007/10/03)
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- 1,6-bis(trimethylsilyl)-3,3,3,4-tetraalkylhexa-1,5-diynes
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Silylacetylene chlorides Me3SiCCCRR'Cl react with magnesium in ether medium to give the corresponding 1,6-bis(trimethylsilyl)-3,3,4,4-tetraalkylhexa-1,5-diynes.By the same method bis(1-trimethylsilylethynylcyclopent-1-yl) and bis(1-trimethylsilylethynylcyclohex-1-yl) were prepared.Desilylation of 1,6-bis(trimethylsilyl)-3,3,4,4-tetraalkylhexa-1,5-diynes gives corresponding 3,3,4,4-tetraalkylhexa-1,5-diynes.
- Yarosh, O. G.,Zhilitskaya, L. V.,Albanov, A. I.,Burnashova, T. D.,Voronkov, M. G.
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p. 547 - 549
(2007/10/03)
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- A Regioselective and Stereospecific Synthesis of Allylsilanes from Secondary Allylic Alcohol Derivatives
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Primary and secondary allylic acetates and benzoates react with the dimethyl(phenyl)silyl-cuprate reagent to give allylsilanes, provided that the THF in which the cuprate is prepared is diluted with ether before addition of the allylic ester.The reaction is reasonably regioselective in some cases: (i) when the allylic system is more-substituted at one end than the other, as in the reactions 4->5 and 9->10; (ii) when the steric hindrance at one end is neopentyl-like, as in the reactions 15->16; and (iii) when the disubstituted double bond has the Z configuration, as in th e reactions Z-19->E-21 or, better, because the silyl group is becoming attached to the less-sterically hindered end of the allylic system, Z-20->E-22.The regioselectivity is better if a phenyl carbamate is used in place of the ester, and a three-step protocol assembling the mixed cuprate on the leaving group is used, as in the reactions 23->24 and E- or Z-29->E-21, or, best of all, because the silyl group is again becoming attached to the less-sterically hindered end of the allylic system, E- or Z-30->E-22.This sequence works well to move the silyl group onto the more substituted end of an allyl system, but only when the move is from a secondary allylic carbamate to a tertiary allylsilane, as in the reaction 38->39.Allyl(trimethyl)silanes can be made using alkyl- or aryl-cuprates on trimethylsilyl-containing allylic esters and carbamates, as in the reactions 40->41, and 43->44.The reaction of the silyl-cuprate with allylic esters and the three-step sequence with the allylic carbamates are stereochemically complementary, the former being stereospecifically anti and the latter stereospecifically syn.Homochiral allylsilanes can be ma de by these methods with high levels of stereospecificity, as shown by the synthesis of the allylsilanes 54, 58 and 59.
- Fleming, Ian,Higgins, Dick,Lawrence, Nicholas J.,Thomas, Andrew P.
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p. 3331 - 3350
(2007/10/02)
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- Ene Reactions of Allylic Derivatives of Silicon, Germanium, Tin and Lead with N-Phenyltriazolinedione: the Effect of Varying the Metal
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The compounds Ph3MCH2CH=CH2 and (M=Si, Ge, Sn or Pb) have been treated with 4-phenyl-1,2,4-triazoline-3,5-dione, and the relative yields of the products of the M-ene reaction, of the H-ene reaction, and of the reaction involving cycloaddition with shift of the organometallic substituent, have been determined.The silicon compounds react principally by the H-ene process.The cycloaddition process is at a maximum (50percent or 70percent) with the germanium compounds, and the tin compounds show mainly the M-ene reaction, with some cycloaddition but no H-ene reaction.Triphenylprop-2-enylplumbane show only the M-ene reaction.In trimethyl(1,1-dimethylprop-2-enyl)silane, in which the H-ene reaction is blocked, only cycloaddition with shift of the silyl group is observed.
- Cai, Jiaqiang,Davies, Alwyn G.
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p. 1743 - 1746
(2007/10/02)
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