- Boron–Nitrogen-Doped Nanographenes: A Synthetic Tale from Borazine Precursors
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In this work, a comprehensive account of the authors’ synthetic efforts to prepare borazino-doped hexabenzocoronenes by using the Friedel–Crafts-type electrophilic aromatic substitution is reported. Hexafluoro-functionalized aryl borazines, bearing an ortho fluoride leaving group on each of the N- and B-aryl rings, was shown to lead to cascade-type electrophilic aromatic substitution events in the stepwise C?C bond formation, giving higher yields of borazinocoronenes than those obtained with borazine precursors bearing fluoride leaving groups at the ortho positions of the B-aryl substituents. By using this pathway, an unprecedented boroxadizine-doped PAH featuring a gulf-type periphery could be isolated, and its structure proven by single-crystal X-ray diffraction analysis. Mechanistic studies on the stepwise Friedel–Crafts-type cyclization suggest that the mechanism of the planarization reaction proceeds through extension of the π system. To appraise the doping effect of the boroxadizine unit on the optoelectronic properties of topology-equivalent molecular graphenes, the all-carbon and pyrylium PAH analogues, all featuring a gulf-type periphery, were also prepared. As already shown for the borazino-doped hexabenzocoronene, the replacement of the central benzene ring by its B3N2O congener widens the HOMO–LUMO gap and dramatically enhances the fluorescence quantum yield.
- Dosso, Jacopo,Battisti, Tommaso,Ward, Benjamin D.,Demitri, Nicola,Hughes, Colan E.,Williams, P. Andrew,Harris, Kenneth D. M.,Bonifazi, Davide
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supporting information
p. 6608 - 6621
(2020/04/22)
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- N2 extrusion and co insertion: A novel palladium-catalyzed carbonylative transformation of aryltriazenes
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A novel procedure for the replacement of N2 with CO of aryltriazenes has been developed. Aryltriazenes were converted to the corresponding arylamides catalyzed by 1 mol % of PdCl2/P(o-Tol)3 under CO pressure. In this process, aryldiazonium salts were generated in the presence of 40 mol % of MeSO3H. Nitrogen was released from the substrates and CO formally inserted. Aryl bromides, iodides, alkynes, and free hydroxyl groups can be tolerated in this transformation.
- Li, Wanfang,Wu, Xiao-Feng
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p. 1910 - 1913
(2015/04/27)
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- Directed Metalation-Suzuki-Miyaura Cross-Coupling Strategies: Regioselective Synthesis of Hydroxylated 1-Methyl-phenanthrenes
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A general, efficient, and regioselective synthesis of a series of hydroxylated 1-methylphenanthrenes 9 by a combined directed ortho metalation (DoM)-Suzuki-Miyaura cross-coupling-directed remote metalation (DreM) sequence is reported. Diversity to this methodology was achieved by a regioselective DoM rather than DreM reaction, affording more highly substituted phenanthrols (Table 2). Application of the turbo-Grignard reagent (i-PrMgCl·LiCl) in the Ni-catalyzed Corriu-Kumada reaction gave efficient decarbamoylation (Tables 3and 4). Additional features are the TMS protecting group and halo-induced ipso-desilylation tactics applied to the regioselective synthesis of phenanthrenes (Scheme 2).
- J?rgensen, K?re B.,Rantanen, Toni,D?rfler, Thilo,Snieckus, Victor
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p. 9410 - 9424
(2015/10/12)
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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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- Simple synthesis of amides and weinreb amides Using PPh3 or PolymerSupported PPh3 and Iodine
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The combination of PPh3/I2 has been shown to be effective for the conversion of a range of carboxylic acids into secondary, tertiary, and Weinreb amides. Simplification of the procedure was possible with the use of polymer-supported PPh3/ I2. Weinreb amides produced with the use of polymer-supported PPh3 could be filtered through a short silica gel plug and used in further transformations. Thus, the use of polymer-supported PPh3 offers potential applicability to diversityoriented reactions. Formal total syntheses of apocynin and pratosine, as well as syntheses of anhydrolychorinone and hippadine, have been achieved through the use of this amide-forming method. An attempt has been made to gain insight into this reaction.
- Kumar, Amit,Akula, Hari Kiran,Lakshman, Mahesh K.
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experimental part
p. 2709 - 2715
(2010/08/05)
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- AMINO SUBSTITUTED DIARYL[A,D]CYCLOHEPTENE ANALOGS AS MUSCARINIC AGONISTS AND METHODS OF TREATMENT OF NEUROPSYCHIATRIC DISORDERS
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Disclosed herein are analogs of clozapine and pharmaceutically acceptable salts, esters, amides, or prodrugs thereof; methods of synthesizing the analogs; and methods of using the analogs for treating neuorpsychiatric disorders. In some embodiments, the analogs are amino substituted diaryl[a,d]cycloheptenes.
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Page/Page column 93
(2008/06/13)
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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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- Potent, orally bioavailable delta opioid receptor agonists for the treatment of pain: Discovery of N,N-diethyl-4-(5-hydroxyspiro-[chromene-2, 4′-piperidine]-4-yl)benzamide (ADL5859)
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Selective δ opioid receptor agonists are promising potential therapeutic agents for the treatment of various types of pain conditions. A spirocyclic derivative was identified as a promising hit through screening. Subsequent lead optimization identified compound 20 (ADL5859) as a potent, selective, and orally bioavailable δ agonist. Compound 20 was selected as a clinical candidate for the treatment of pain.
- Le Bourdonnec, Bertrand,Windh, Rolf T.,Ajello, Christopher W.,Leister, Lara K.,Gu, Minghua,Chu, Guo-Hua,Tuthill, Paul A.,Barker, William M.,Koblish, Michael,Wiant, Daniel D.,Graczyk, Thomas M.,Belanger, Serge,Cassel, Joel A.,Feschenko, Marina S.,Brogdon, Bernice L.,Smith, Steven A.,Christ, David D.,Derelanko, Michael J.,Kutz, Steve,Little, Patrick J.,DeHaven, Robert N.,DeHaven-Hudkins, Diane L.,Dolle, Roland E.
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supporting information; experimental part
p. 5893 - 5896
(2009/10/17)
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- USE OF N-DESMETHYLCLOZAPINE AND RELATED COMPOUNDS AS DOPAMINE STABILIZING AGENTS
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Disclosed herein is the use of N-desmethylclozapine (NDMC) and related compounds to treat a variety of neuropsychiatric diseases including psychosis. It is shown that NDMC and related compounds are agonists or partial agonists at D2 and D3 dopamine receptors and thus may be effective as a dopamine stabilizing agent, allowing it to be used to treat or provide reduced incidence of Extrapyramidal symptoms (EPS) and/or tardive dyskinesias (TD). Also disclosed is administering NDMC and related compounds in combination with other anti-psychotic agents.
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Page/Page column 110
(2010/11/24)
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- AMINO SUBSTITUTED DIARYL[A,D]CYCLOHEPTENE ANALOGS AS MUSCARINIC AGONISTS AND METHODS OF TREATMENT OF NEUROPSYCHIATRIC DISORDERS
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Disclosed herein are analogs of clozapine and pharmaceutically acceptable salts, esters, amides, or prodrugs thereof; methods of synthesizing the analogs; and methods of using the analogs for treating neuorpsychiatric disorders. In some embodiments, the analogs are amino substituted diaryl[a,d]cycloheptenes.
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Page/Page column 90
(2008/06/13)
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- 2-(Bicyclo)alkylamino-derivatives as mediatores of chronic pain and inflammation
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Compounds disclosed herein are bradykinin B1 antagonist compounds useful in the treatment or prevention of symptoms such as pain and inflammation associated with the bradykinin B1 pathway.
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Page/Page column 17; 26
(2008/06/13)
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- Ortho-metalated aromatic tertiary amides: New synthetic applications
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Ortho-lithio-cuprate species derived from aromatic tertiary amides exhibited a significantly larger field of application than the lithio precursor.
- Casas, Ramon,Cave, Christian,D'Angelo, Jean
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p. 1039 - 1042
(2007/10/02)
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- Directed ortho metalation of n,n-diethyl benzamides. Methodology and regiospecific synthesis of useful contiguously tri- and tetra-substituted oxygenated aromatics, phthalides and phthalic anhydrides
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Full experimental details for the directed ortho metalation approch to a variety of simple ortho-substituted N,N-diethyl benzamides (Table 1) and contiguously 1,2,3- and 1,2,3,4-substituted benzamides (Tables 2) are given. The efficient conversion of these benzamides (6, 10, 12, 13, 18, 19) into phthalides (9a-b, 16b-c, 17) and phthalic anhydrides (8,16a), compounds previously available by demanding, classical methods, is detailed. A short synthesis of iso-ochracinic acid (27) is described.
- De Silva,Reed,Billedeau,Wang,Norris,Snieckus
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p. 4863 - 4878
(2007/10/02)
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- INVESTIGATIONS ON N,N-DIALKYLBENZAMIDES BY NMR SPECTROSCOPY. PART IV. COMPARISON OF BARRIERS TO ROTATION ABOUT THE AMINE C-N BOND IN ORTHO-SUBSTITUTED N,N-DIMETHYL-AND N,N-DIETHYLBENZAMIDES
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The barriers to rotation about the amide C-N bond in a series of ortho-substituted N,N-dimethyl and N,N-diethylbenzamides have been compared.It has been stated that for most of substituents, namely CH3, Cl, Br, I and NO2, the rates of rotation in both series of compounds are identical within the accuracy of measurement (kEt/kMe ca.1).The remaining compounds (F, CN, CH3) show a higher rate of rotation in the series of diethylbenzamides (kEt/kMe ca.1,5).An exception are the OH derivatives in which the internal H-bond is present and because of that the barrier to rotation is lowered and the kEt/kMe ratio raised up to 2.3.
- Gryf-Keller, Adam,Terpinski, Jacek,Zajaczkowska-Terpinska, Ewa
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p. 429 - 434
(2007/10/02)
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