- Functionalization of Bis-Diazaphospholene P–P Bonds with Diverse Electrophiles
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Phosphorus-sp3 or -sp2 carbon bonds are readily formed by the reaction of bis-diazaphospholenes with several classes of electrophiles. These reactions result in cleavage of the phosphorus–phosphorus bond and formation of functionalized diazaphospholenes. The reactions proceed rapidly, without catalysis. Experimental evidence with aryl and alkyl halides suggests the intermediacy of radicals in some cases, however other evidence suggests either radical or polar mechanisms may be operative for certain substrates, with a dependence on reaction conditions. In three cases, the product aryl diazaphospholenes have been shown to transfer the aryl substituent to electrophiles. These results reveal that diazaphospholene dimers are potent participants in radical chemistry with organic substrates at room temperature without requiring chemical initiators.
- Huchenski, Blake S. N.,Robertson, Katherine N.,Speed, Alexander W. H.
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- Electron transfer-induced coupling of haloarenes to styrenes and 1,1-diphenylethenes triggered by diketopiperazines and potassium tert-butoxide
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The coupling of haloarenes to styrenes and 1,1-diarylethenes has been achieved with potassium tert-butoxide in the presence of N,N'-dialkyldiketopiperazines. In contrast to previously reported reactions where phenanthroline has been used to mediate the reactions, the use of diketopiperazines can lead to either 1,1,2-triarylethenes or 1,1,2-triarylethanes, depending on the conditions used.
- Doni, Eswararao,Zhou, Shengze,Murphy, John A.
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- Site-Specific Oxidation of (sp3)C-C(sp3)/H Bonds by NaNO2/HCl
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A site-specific oxidation of (sp3)C-C(sp3) and (sp3)C-H bonds in aryl alkanes by the use of NaNO2/HCl was explored. The method is chemical-oxidant-free, transition-metal-free, uses water as the solvent, and proceeds under mild conditions, making it valuable and attractive to synthetic organic chemistry.
- Zhao, Jianyou,Shen, Tong,Sun, Zhihui,Wang, Nengyong,Yang, Le,Wu, Jintao,You, Huichao,Liu, Zhong-Quan
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supporting information
p. 4057 - 4061
(2021/05/26)
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- Nickel-Catalyzed Asymmetric Reductive 1,2-Carboamination of Unactivated Alkenes
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Starting from diverse alkene-tethered aryl iodides and O-benzoyl-hydroxylamines, the enantioselective reductive cross-electrophilic 1,2-carboamination of unactivated alkenes was achieved using a chiral pyrox/nickel complex as the catalyst. This mild, modular, and practical protocol provides rapid access to a variety of β-chiral amines with an enantioenriched aryl-substituted quaternary carbon center in good yields and with excellent enantioselectivities. This process reveals a complementary regioselectivity when compared to Pd and Cu catalysis.
- He, Jun,Xue, Yuhang,Han, Bo,Zhang, Chunzhu,Wang, You,Zhu, Shaolin
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p. 2328 - 2332
(2020/01/08)
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- Synthesis of All-Carbon Quaternary Centers by Palladium-Catalyzed Olefin Dicarbofunctionalization
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The redox-neutral dicarbofunctionalization of tri- and tetrasubstituted olefins to form a variety of (hetero)cyclic compounds under photoinduced palladium catalysis is described. This cascade reaction process was used to couple styrenes or acryl amides with a broad range of highly decorated olefins tethered to aryl or alkyl bromides (>50 examples). This procedure enables one or two contiguous all-carbon quaternary centers to be formed in a single step. The products could be readily diversified and applied in the synthesis of a bioactive oxindole analogue.
- Koy, Maximilian,Bellotti, Peter,Katzenburg, Felix,Daniliuc, Constantin G.,Glorius, Frank
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supporting information
p. 2375 - 2379
(2020/01/24)
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- From ynamides to highly substituted benzo[b]furans: Gold(I)-catalyzed 5-endo-dig-cyclization/rearrangement of alkylic oxonium intermediates
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A series of arylynamides with alkyloxy groups at the ortho position of the aryl group was prepared through a short alkylation/cross-coupling/amidation sequence. The gold-catalyzed conversion of these substrates combined both C-O and C-C formation steps, thus providing benzofurans with amine functionalities at the 2-position and alkyl groups at the 3-position. Cross-over experiments showed that the alkyl-migration step was an intermolecular process. X-ray crystal-structure analysis of two of the products supported our structural assignment. In some cases, the corresponding benzofurans without the alkyl group at the 3-position were obtained as side-products, which were formed through a competing protodeauration process. Golden touch: Arylynamides with o-alkyloxy groups were prepared through an alkylation/cross-coupling/amidation sequence. Their Au-catalyzed conversion provided benzofurans with amine groups at the 2-position and alkyl groups at the 3-position. Copyright
- Blanco Jaimes, Maria Camila,Weingand, Vanessa,Rominger, Frank,Hashmi, A. Stephen K.
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supporting information
p. 12504 - 12511
(2013/09/23)
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- Photoredox transformations with dimeric gold complexes
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Let the sunshine in! Unactivated alkyl and aryl bromides underwent a light-enabled reductive radical cyclization in the presence of a dimeric phosphine-gold complex as a photocatalyst (see scheme; X=C(CO 2Et)2, NR, O). Sunlight can be used as the energy source for this simple and efficient radical reaction, which does not require potentially hazardous and toxic chemical reagents, such as organostannanes and chemical initiators.
- Revol, Guillaume,McCallum, Terry,Morin, Mathieu,Gagosz, Fabien,Barriault, Louis
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supporting information
p. 13342 - 13345
(2014/01/06)
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- Gold-catalyzed diastereoselective [2+2+2]-cycloaddition of 1,7-enynes with carbonyl compounds
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We report a gold-catalyzed [2+2+2]-cycloaddition of 1,7-enynes with carbonyl species; our experimental data suggest that the resulting oxacyclic cycloadducts arose from an interception of gold-containing cyclobutenium intermediates with carbonyl species.
- Huple, Deepak B.,Liu, Rai-Shung
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supporting information
p. 10975 - 10977
(2013/01/15)
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- THERAPEUTIC AGENTS, AND METHODS OF MAKING AND USING THE SAME
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In part, the present invention is directed towards compounds with FabI inhibiting properties. Such compounds may also inhibit other enzymes, including those similar to FabI either structurally or functionally, for example, Fab K. Kits and compositions that include the disclosed compounds are also provided. Methods of treating a subject with a bacterial illness is also disclosed.
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Page/Page column 167
(2008/06/13)
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- THERAPEUTIC AGENTS, AND METHODS OF MAKING AND USING THE SAME
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In part, the present invention is directed to antibacterial compounds
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Page/Page column 170
(2010/11/27)
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- Indium-catalyzed radical reductions of organic halides with hydrosilanes
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(Equation Presented) The In(OAc)3-catalyzed reaction of bromo- and iodoalkanes with PhSiH3 in THF at 70°C gave dehalogenated alkanes in good to high yields. In the presence of Et3B and air, the reduction proceeded smoothly at 30°C. When 2,6-lutidine and air were used as additives, the In(OAc)3-catalyzed system enabled an efficient reduction of simple and functionalized iodoalkanes in EtOH. Catalytic use of GaCl3 was found to be effective in the reduction of haloalkanes with poly(methylhydrosiloxane) (PMHS). These catalytic reductions probably involve a radical chain mechanism in which indium or gallium hydride species work as the actual reductants.
- Miura, Katsukiyo,Tomita, Mitsuru,Yamada, Yusuke,Hosomi, Akira
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p. 787 - 792
(2007/10/03)
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- Regioselective synthesis of substituted 1-indanols, 2,3-dihydrobenzofurans and 2,3-dihydroindoles by electrochemical radical cyclization using an arene mediator
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Electrochemical reduction of haloarenes carrying 2-(1-hydroxybut-3-enyl), 2-allyloxy or N-allyl-N-methylamino group in the presence of phenanthrene as a mediator generated the corresponding aryl radicals and gave the corresponding 5-exo cyclization produc
- Kurono, Nobuhito,Honda, Eiichi,Komatsu, Fumikazu,Orito, Kazuhiko,Tokuda, Masao
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p. 1791 - 1801
(2007/10/03)
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- The samarium grignard reaction. In situ formation and reactions of primary and secondary alkylsamarium(III) reagents
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This work shows that primary and secondary radicals are rapidly reduced in THF/HMPA to form primary- and secondary-alkylsamarium reagents. The primary- and secondary-radicals can be formed either by direct SmI2 reduction of primary- and secondary-halides or by a previous rapid radical cyclization. The samarium reagents have moderate stability in solution, and they react with a variety of typical electrophiles, including aldehydes and ketones. The work further shows that organosamarium intermediates can be involved in the traditional samarium Barbier reaction of aldehydes and ketones conducted in THF/HMPA. A new procedure called the "samarium Grignard" method is introduced, and it is suggested that this new procedure will have considerably more scope and generality than the samarium Barbier reaction.
- Curran, Dennis P.,Totleben, Michael J.
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p. 6050 - 6058
(2007/10/02)
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