- Identification of key functionalization species in the Cp?Ir(iii)-catalyzed-: ortho halogenation of benzamides
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Cp?Ir(iii) complexes have been shown to be effective for the halogenation of N,N-diisopropylbenzamides with N-halosuccinimide as a suitable halogen source. The optimized conditions for the iodination reaction consist of 0.5 mol% [Cp?IrCl2]2 in 1,2-dichlor
- Brown, Caleb A.,Guzmán Santiago, Alexis J.,Ison, Elon A.,Sommer, Roger D.
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supporting information
p. 16166 - 16174
(2020/12/03)
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- Directed: Ortho-metalation-nucleophilic acyl substitution strategies in deep eutectic solvents: The organolithium base dictates the chemoselectivity
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Directed ortho metalation (DoM) or nucleophilic acyl substitution (SNAc) can be efficiently programmed on the same aromatic carboxylic acid amide, in a choline chloride-based eutectic mixture, by simply switching the nature of the organolithium reagent. Telescoped, one-pot ortho-lithiation/Suzuki-Miyaura cross-couplings have also been demonstrated for the first time in Deep Eutectic Solvents.
- Ghinato, Simone,Dilauro, Giuseppe,Perna, Filippo Maria,Capriati, Vito,Blangetti, Marco,Prandi, Cristina
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supporting information
p. 7741 - 7744
(2019/07/12)
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- Amide Effects in C?H Activation: Noncovalent Interactions with L-Shaped Ligand for meta Borylation of Aromatic Amides
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A new concept for the meta-selective borylation of aromatic amides is described. It has been demonstrated that while esters gave para borylations, amides lead to meta borylations. For achieving high meta selectivity, an L-shaped bifunctional ligand has been employed and engages in an O???K noncovalent interaction with the oxygen atom of the moderately distorted amide carbonyl group. This interaction provides exceptional control for meta C?H activation/borylation.
- Bisht, Ranjana,Hoque, Md Emdadul,Chattopadhyay, Buddhadeb
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p. 15762 - 15766
(2018/11/10)
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- Efficient modulation of γ-aminobutyric acid type a receptors by piperine derivatives
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Piperine activates TRPV1 (transient receptor potential vanilloid type 1 receptor) receptors and modulates γ-aminobutyric acid type A receptors (GABAAR). We have synthesized a library of 76 piperine analogues and analyzed their effects on GABAAR by means of a two-microelectrode voltage-clamp technique. GABAAR were expressed in Xenopus laevis oocytes. Structure-activity relationships (SARs) were established to identify structural elements essential for efficiency and potency. Efficiency of piperine derivatives was significantly increased by exchanging the piperidine moiety with either N,N-dipropyl, N,N-diisopropyl, N,N-dibutyl, p-methylpiperidine, or N,N-bis(trifluoroethyl) groups. Potency was enhanced by replacing the piperidine moiety by N,N-dibutyl, N,N-diisobutyl, or N,N-bistrifluoroethyl groups. Linker modifications did not substantially enhance the effect on GABAAR. Compound 23 [(2E,4E)-5-(1,3-benzodioxol-5-yl)-N,N-dipropyl-2,4-pentadienamide] induced the strongest modulation of GABAA (maximal GABA-induced chloride current modulation (IGABA-max = 1673% ± 146%, EC 50 = 51.7 ± 9.5 μM), while 25 [(2E,4E)-5-(1,3-benzodioxol- 5-yl)-N,N-dibutyl-2,4-pentadienamide] displayed the highest potency (EC 50 = 13.8 ± 1.8 μM, IGABA-max = 760% ± 47%). Compound 23 induced significantly stronger anxiolysis in mice than piperine and thus may serve as a starting point for developing novel GABA AR modulators.
- Sch?ffmann, Angela,Wimmer, Laurin,Goldmann, Daria,Khom, Sophia,Hintersteiner, Juliane,Baburin, Igor,Schwarz, Thomas,Hintersteininger, Michael,Pakfeifer, Peter,Oufir, Mouhssin,Hamburger, Matthias,Erker, Thomas,Ecker, Gerhard F.,Mihovilovic, Marko D.,Hering, Steffen
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supporting information
p. 5602 - 5619
(2014/08/05)
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- Ruthenium-catalyzed ortho-C-H halogenations of benzamides
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[Ru3(CO)12] and AgO2C(1-Ad) enabled the first ruthenium-catalyzed intermolecular halogenations of arenes via C-H activation. Thereby, brominations and iodinations of electron-rich and electron-deficient benzamides were ach
- Wang, Lianhui,Ackermann, Lutz
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supporting information
p. 1083 - 1085
(2014/01/17)
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- Employing a robustness screen: Rapid assessment of rhodium(III)-catalysed C-H activation reactions This paper is dedicated to Professor Paul A. Wender, a great scientist, teacher and mentor
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Following the discovery of new synthetic methodology, an assessment of its potential utility in real synthetic problems is highly desirable to facilitate its application. Herein, we describe an assessment of two contemporary rhodium catalysed C-H activati
- Collins, Karl D.,Glorius, Frank
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p. 7817 - 7825
(2013/08/23)
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- Nickel or phenanthroline mediated intramolecular arylation of sp 3 C-H bonds using aryl halides
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The development of the intramolecular arylation of sp3 C-H bonds adjacent to nitrogen using aryl halides is described. Arylation was accomplished using either Ni(COD)2 or 1,10-phenanthroline in substoichiometric amounts, and the reaction conditions were applied to a variety of electronically differentiated benzamide substrates. Preliminary studies suggest a mechanism involving aryl and alkyl radical intermediates.
- Wertjes, William C.,Wolfe, Lydia C.,Waller, Peter J.,Kalyani, Dipannita
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supporting information
p. 5986 - 5989
(2014/01/06)
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- High-yielding, versatile, and practical [Rh(III)Cp*]-catalyzed ortho bromination and iodination of arenes
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We report a uniquely high-yielding, general, and practical ortho bromination and iodination reaction of different classes of aromatic compounds. This reaction occurs by Rh(III)-catalyzed C-H bond activation methodology and is therefore the first example of the application of this cationic catalyst for C-Br and C-I bond formation.
- Schroeder, Nils,Wencel-Delord, Joanna,Glorius, Frank
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supporting information; experimental part
p. 8298 - 8301
(2012/06/29)
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- BENZOFLUORENE COMPOUND AND USE THEREOF
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A novel material having high hole-transporting ability and a high glass transition temperature and having long-lasting durability is obtained. A benzofluorene compound represented by formula (1) is used. (In the formula, M is a substituted or unsubstituted aryl group having 6-40 carbon atoms or a substituted or unsubstituted heteroaryl group having 5-40 carbon atoms; Ar1 to Ar4 each independently is a substituted or unsubstituted aryl group having 6-40 carbon atoms or a substituted or unsubstituted heteroaryl group having 5-40 carbon atoms, provided that at least one of Ar1 to Ar4 is a substituent represented by any of the following formulae (2) to (5); and p is an integer of 0-2.) (In the formulae, R1 to R4 each independently is a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a linear, branched, or cyclic alkyl group, a linear, branched, or cyclic alkoxy group, a substituted or unsubstituted aryl group having 6-40 carbon atoms, or a substituted or unsubstituted aryloxy group having 6-40 carbon atoms, provided that R1 and R2 may be bonded to each other to form a ring.)
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Page/Page column 26; 27
(2009/01/24)
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- Carbanionic friedel-crafts equivalents. Regioselective directed Ortho and remote metalation-C-N cross coupling routes to acridones and dibenzo[b,f]azepinones
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(Chemical Equation Presented) Carbanion-mediated general regioselective routes to acridones 4 (Table 2) and dibenzo[b,f]azepinones 20 (Table 4) are described. Buchwald-Hartwig C-N cross coupling of o-halo benzamides 1 with anilines 2 or 16, followed by simple N-methylation, dependably provides N-methyl diarylamines 3 (Table 1) and 18 (Table 3). Upon treatment with LDA, 3 and 18 are converted into acridones 4 and dibenzo[b,f]azepinones 20, respectively, in good to excellent yields with regioselectivity which depends upon the presence or absence of directed metalation groups (DMGs). Brief investigations as follows are described: the synthesis of desmethyl acridone 15 (Scheme 4), an attempt to effect a double-directed remote metalation sequence which leads only to a monocyclization product 13 (Scheme 3), and an analogous but nonregioselective route to a xanthone 22 and dibenzo[b,f]oxepinone 24 (Scheme 5). DFT calculations reveal low energy conformations for compounds 18b and 23 which account for product formation and indicate that the cyclization reactions are under kinetic control.
- MacNeil, Stephen L.,Gray, Matthew,Gusev, Dmitry G.,Briggs, Laura E.,Snieckus, Victor
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supporting information; experimental part
p. 9710 - 9719
(2009/04/07)
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- The Tertiary Amide as an Effective Director of Ortho Lithiation
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The tertiary amides N,N-diethylbenzamide (1) and N,N-diisopropylbenzamide (3) give the ortho-lithiated species 2 on treatment with sec-BuLi/TMEDA or n-BuLi/TMEDA, respectively, at -78 deg.Lithiation of 1 followed by rection with either methyl iodide, ethyl iodide, benzophenone, acetone, benzaldehyde, or trimethoxyborane-hydrogen peroxide gives the expected ortho substituted product.Intramolecular competition between the diethyloamido and chloro, methoxyl, sulfonamido, (dimethylamino)methyl, or oxazolino functions in ortho- and para-substituted benzamides establishes the tertiary amido group to be more effective in directing metalation than any noncarboxamide functional group under the prescribed conditions.Complimentarity of directing effects is observed with the chloro and methoxyl groups in the meta-substituted diethylbenzamides but not with the methyl group.The secondary amide is found to have a directing ability comparable to the tertiary amide with sec-BuLi/TMEDA at -78 deg in THF although the yields are low. 13C NMR chemical shifts are particularly useful for the structural assignments which are confirmed chemically by lactonization of some products.A labeling study with N,N-diisopropyl-2,6-dideuteriobenzamide suggests that lithiation of the ortho position of 3 is direct and not the result of rearrangement of an initially formed α-aza anion.Control of metalation at the ortho or benzylic position by proper selection of the organolithium base is illustrated for N,N-diisopropyl-p-toluamide.The value of the tertiary amide for control of ortho lithiations and regiospecific aromatic substitutions is noted.
- Beak, Peter,Brown, Roger A.
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