- C–H Arylation of N-Heteroarenes under Metal-Free Conditions and its Application towards the Synthesis of Pentabromo- and Pentachloropseudilins
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Herein, we are reporting metal-free conditions for radical initiation and direct C–H arylation of N-heteroarenes. Starting from aniline, the corresponding arenediazonium salt generated in situ is reduced to an aryl radical in the presence of chloropromazine hydrochloride, a new reagent for this application. The optimized procedures are mild, operationally simple, and are working successfully with more diverse substrates in comparison to reported methods. The optimized method is also employed for the synthesis of marine natural products Pentabromo- and Pentachloropseudilins (PBP/PCP). In the present study, we also validated the potential of the Pentachloropseudilin (PCP), thus synthesized, for inhibition of Myosin1 function in mammalian cells and confirmed that PCP phenocopies Myosin1c depletion in cells.
- Kumar, Mukesh,Sharma, Shweta,Sil, Parijat,Kushwaha, Manoj,Mayor, Satyajit,Vishwakarma, Ram A.,Singh, Parvinder Pal
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supporting information
p. 3591 - 3598
(2019/06/20)
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- Cercosporin-bioinspired photoreductive activation of aryl halides under mild conditions
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Bioinspired by the naturally-occurring cercosporin-driven infection process of plant pathogenic fungi Cercospora sp., here we took advantage of the photophysical properties of cercosporin, and used it as a metal-free photocatalyst to develop an unpreceden
- Tang, Zhaocheng,Li, Jia,Lin, Fulin,Bao, Wenhao,Zhang, Shiwei,Guo, Baodang,Huang, Shuping,Zhang, Yan,Rao, Yijian
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- Silver(I)-catalyzed route to pyrroles: Synthesis of halogenated pseudilins as allosteric inhibitors for myosin atpase and x-ray crystal structures of the protein-inhibitor complexes
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The pentahalogenated 2-arylpyrrole-type alkaloids pentabromopseudilin and pentachloropseudilin represent a new class of isoform-specific allosteric inhibitors of myosin ATPase. Herein, we describe an application of the silver(I)-catalyzed cycloisomerizati
- Martin, Rene,Risacher, Celia,Barthel, Andre,Jaeger, Anne,Schmidt, Arndt W.,Richter, Sabine,Boehl, Markus,Preller, Matthias,Chinthalapudi, Krishna,Manstein, Dietmar J.,Gutzeit, Herwig O.,Knoelker, Hans-Joachim
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p. 4487 - 4505
(2014/08/05)
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- Synthesis, solid-state analyses, and anion-binding properties of meso-aryldipyrrin-5,5′-diylbis(phenol) and -bis(aniline) ligands
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The design of new molecular scaffolds for the selective recognition or transport of anions is often critical, because subtle changes in the substitution pattern may drastically impact the targeted properties. Herein, detailed spectroscopic and X-ray crystal-structure analyses were used to investigate the effect of the substitution pattern of a new series of N 2O2 or N4 anion sensors. Our study evidences two distinct in-in and in-out conformations depending on the nature of the substituent (e.g., phenol vs. aniline). Interestingly, because of intramolecular hydrogen bonds involving the -OH or the -NH2 functions, the dipyrrin subunit only acts as a scaffold and does not participate in the anion binding. Furthermore, the nature of the meso substituent was not critical, as similar binding affinities were measured for meso-C6H5 or meso-C6F5 ligands. Hence, the meso position can be further modified without any noticeable changes to the electron density on the dipyrromethene subunit.
- Copey, Laurent,Jean-Gerard, Ludivine,Framery, Eric,Pilet, Guillaume,Andrioletti, Bruno
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supporting information
p. 4759 - 4766
(2014/08/05)
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- Copper-catalyzed 5-endo-trig cyclization of ketoxime carboxylates: A facile synthesis of 2-arylpyrroles
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A novel and facile copper-catalyzed 5-endo-trig cyclization of ketoxime carboxylates for the synthesis of 2-arylpyrroles has been developed. The reaction tolerates a range of functional groups and is a practical procedure for rapid synthesis of 2-arylpyrroles in high yields under mild conditions. the Partner Organisations 2014.
- Du, Wei,Zhao, Mi-Na,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
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p. 7437 - 7439
(2014/07/07)
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- Synthesis of pentabromopseudilin and other arylpyrrole derivatives via Heck arylations
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Pentrabromopseudilin and other 2 and 3-arylpyrrole derivatives were synthesized through the Heck-Matsuda reaction involving endocyclic enecarbamates and N-protected 3-pyrrolines, respectively. The overall processes permitted an easy and efficient access t
- Schwalm, Cristiane S.,De Castro, Ilton B.D.,Ferrari, Jailton,De Oliveira, Fábio L.,Aparicio, Ricardo,Correia, Carlos Roque D.
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p. 1660 - 1663
(2012/04/10)
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- Optimization of the Suzuki coupling reaction in the synthesis of 2-[(2-substituted)phenyl]pyrrole derivatives
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A facile three-step synthesis of 2-(2-aminophenyl)pyrrole (1) and 2-[(2-aminomethyl)phenyl]pyrrole (2) is reported by use of Suzuki coupling of N-Boc-pyrrol-2-yl boronic acid (3) and o-substituted aryl halogenides, followed by hydrogenation. The Pd-catalyzed cross-coupling reaction is optimized to be applicable to a wide range of substitued aryl halogenides, with electron-donating and electron-withdrawing substituents, 5a-g. Moreover, Pd-catalyzed coupling of o-bromoaniline and 3 could be applied for the one-step preparation of pyrrolo[1,2-c]quinazolin-5(6H)-one (8). Copyright
- Aleskovic, Marija,Basaric, Nikola,Mlinaric-Majerski, Kata
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experimental part
p. 1329 - 1335
(2012/01/04)
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- Dipyrrinphenol-Mn(iii) complex: Synthesis, electrochemistry, spectroscopic characterisation and reactivity
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Herein, we report the manganese complex with a novel trianionic ligand, the pentafluorophenyldipyrrinphenol ligand DPPH3. The X-ray crystal structure reveals that the MnIII complex exists in a dimeric form in the solid state. Electrochemical studies indicate two quasi-reversible one electron oxidation processes. EPR data on the one electron oxidised species in solution support the formation of a monuclear Mn complex with an S = 3/2 spin system. Preliminary studies towards epoxidation reactions were tested in the presence of iodosylbenzene (PhIO) and are in favour of an oxygen-atom-transfer (OAT) reaction catalyzed by the MnIII complex.
- El Ghachtouli, Sanae,Wojcik, Karolina,Copey, Laurent,Szydlo, Florence,Framery, Eric,Goux-Henry, Catherine,Billon, Laurianne,Charlot, Marie-France,Guillot, Regis,Andrioletti, Bruno,Aukauloo, Ally
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supporting information; scheme or table
p. 9090 - 9093
(2011/11/14)
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- Triethanolamine-mediated palladium-catalyzed regioselective C-2 direct arylation of free NH-pyrroles
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An atom-economical phosphane-free palladium-catalyzed direct C-2 arylation of unactivated free NH-pyrroles is devised. This method provides a straithforward route to a wide variety of substituted 2-aryl-1H-pyrroles from readily accessible starting materials. Iodoarenes bearing electron-withdrawing and electron-donating substituents are tolerated under the presented reaction conditions. The scope of the reaction is also expanded to N-aryl and -alkylpyrroles albeit in lower yields.
- Jafarpour, Farnaz,Rahiminejadan, Soraya,Hazrati, Hamideh
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supporting information; experimental part
p. 3109 - 3112
(2010/07/15)
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- Alkoxy-substituted derivatives of π-conjugated acyclic anion receptors: Effects of substituted positions
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The synthesis, solid-state assemblies, and anion binding affinities of π-conjugated acyclic anion receptors with alkoxyphenyl substituents are discussed. The position of the alkoxy moiety is essential to determining not only the electronic state but also the anion binding affinity. Copyright
- Maeda, Hiromitsu,Eifuku, Nazuki
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supporting information; experimental part
p. 208 - 209
(2010/03/01)
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- Total synthesis of pentabromo- and pentachloropseudilin, and synthetic analogues-allosteric inhibitors of myosin ATPase
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Stopping myo: The total syntheses of the title compounds have been achieved using a highly efficient silver(I)- catalyzed cyclization of N-tosyl-homopropargylamines. The pseudilin derivatives represent a novel class of myosin inhibitors. A new allosteric
- Martin, Rene,Jaeger, Anne,Bohl, Markus,Richter, Sabine,Fedorov, Roman,Manstein, Dietmar J.,Gutzeit, Herwig O.,Knolker, Hans-Joachim
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scheme or table
p. 8042 - 8046
(2010/01/16)
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- Convenient access to 2-arylpyrroles from 2-lithio-N,N- dibenzylcyclopropylamine and nitriles
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N,N-Dibenzylaminocyclopropyl ketimines formed as intermediates upon treatment of 2-lithiated N,N-dibenzylcyclopropylamines with nitriles, being donor-acceptor-substituted cyclopropanes, immediately underwent ring-enlarging rearrangement and 1,2-elimination of dibenzylamine to produce 2-substituted pyrroles in good yields (14 examples, 55-80%). Georg Thieme Verlag Stuttgart.
- Tanguy, Chloé,Bertus, Philippe,Szymoniak, Jan,Larionov, Oleg V.,De Meijere, Armin
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p. 2339 - 2341
(2007/10/03)
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- Gold(I)-catalyzed intramolecular acetylenic Schmidt reaction
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Substituted pyrroles were prepared by a gold(I)-catalyzed acetylenic Schmidt reaction of homopropargyl azides. The reaction allows for regiospecific substitution at each position of the pyrrole ring under mild conditions. A mechanism in which azides serve as nucleophiles toward gold(I)-activated alkynes with subsequent gold(I)-aided expulsion of dinitrogen is proposed. Copyright
- Gorin, David J.,Davis, Nicole R.,Toste, F. Dean
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p. 11260 - 11261
(2007/10/03)
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- A re(V)-catalyzed C-N bond-forming route to human lipoxygenase inhibitors
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(Chemical Equation Presented) A regioselective synthesis of propargylamines by the coupling of propargyl alcohols with tosylamines and carbamates catalyzed by an air-and moisture-tolerant rhenium-oxo complex is described. The ability to couple functionali
- Ohri, Rachana V.,Radosevich, Alexander T.,Hrovat, K. James,Musich, Christine,Huang, David,Holman, Theodore R.,Toste, F. Dean
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p. 2501 - 2504
(2007/10/03)
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- 3,5-diaryl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dyes: Synthesis, spectroscopic, electrochemical, and structural properties
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This research was undertaken to obtain new 'BODIPY' dyes that fluoresce at relatively long wavelengths. The title compounds 1a-e were prepared via a divergent route involving Suzuki couplings of arylboronic acids to N-tert- butoxycarbonyl-4-bromopyrrole 2, condensation of the products with an acid chloride, and incorporation of the boron difluoride entity. Two alkyl- substituted systems 7a and 7b were also prepared for comparison; the critical difference between structures 1 and 7 is that the former have an aryl group attached to each pyrrole nucleus whereas the latter only have alkyl substituents on that same ring. UV absorption and fluorescence emission data were compared for compounds 1 and 7. Absorption and fluorescence emission maxima for compounds 1 occur at higher wavelengths than for compounds 7, and the Stokes shifts for the aryl-substituted compounds 1 are larger than for the alkyl-substituted compounds 7. Fluorescence quantum yields measured for compounds 1 are less than for compounds 7, and possible reasons for this are outlined. Other physical data for the compounds were also collected. Oxidation and reduction potentials of the systems were obtained from cyclic voltammetry experiments, and a single-crystal X-ray structure determination was performed for the bisnaphthyl-substituted compound 1b.
- Burghart, Armin,Kim, Heejin,Welch, Mike B.,Thoresen, Lars H.,Reibenspies, Joe,Burgess, Kevin,Bergstroem, Fredrik,Johansson, Lennart B.-A.
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p. 7813 - 7819
(2007/10/03)
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- A Novel [3+2] Cycloaddition Approach to Nitrogen Heterocycles via Phosphine-Catalyzed Reactions of 2,3-Butadienoates or 2-Butynoates and Dimethyl Acetylenedicarboxylate with Imines: A Convenient Synthesis of Pentabromopseudilin
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The reactivity of a new three carbon synthon, generated in situ from the reaction of 2,3-butadienoates 2-butynoates with an appropriate phosphine as the catalyst, toward the electron-deficient imines is described. Triphenylphosphine-catalyzed reaction of methyl 2,3-butadienoate with N-sulfonylimines gave the single [3+2] cycloadduct in excellent yield; tributylphosphine-catalyzed reaction of methyl 2,3-butadienoate or 2-butynoate with N-tosylimines afforded the corresponding [3+2] cycloadduct as the major product along with a small amount of the three components adduct. Aliphatic N-tosylimines gave moderate yield for this reaction. In addition, a new phosphine-catalyzed cyclization reaction of dimethyl acetylenedicarboxylate with N-tosylimines is also described. A reaction mechanism is proposed. Further elaborations of the cycloaddition products and the synthesis of pentabromopseudilin using this method are exemplified.
- Xu, Zhenrong,Lu, Xiyan
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p. 5031 - 5041
(2007/10/03)
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- Marine Bacteria, I. - Synthesis of Pentabromopseudiline, a Cytotoxic Phenylpyrrole from Alteromonas luteo-violaceus
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A new synthesis of 2,3,4-tribromo-5-(3,5-dibromo-2-hydroxyphenyl)pyrrole (1a, pentabromopseudiline), an antibiotic, enzymeinhibitory and cytotoxic active constituent of the marine bacterium Alteromonas luteo-violaceus, is described.For investigation of structure-activity relationships further 2-phenylpyrroles are investigated.Key step in their synthesis is the Grignard reaction of 2-(1,3-dioxan-2-yl)ethylmagnesium bromide (9d) with benzoyl chlorides yielding γ-phenyl-γ-ketoaldehydes 24, and the Paal-Knorr cyclisation of the latter. - Key Words: Alteromonas luteo-violaceus / Bromopyrrole / Marine bacteria / Pentabromopseudiline
- Laatsch, Hartmut,Pudleiner, Heinz
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p. 863 - 882
(2007/10/02)
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- NEW METHODS FOR THE SYNTHESIS OF 2-ARYLPYRROLES
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Two short and efficient synthetic approaches for -mostly unknown- 2-arylpyrroles are presented.The key intermediates 3 are conveniently obtained from commercially available acetophenones 5 (method I) or benzoic acid derivatives 10, 11 (method II).
- Kruse, Chris G.,Bouw, Jan P.,Hes, Roelof van,Kuilen, Aalt van de,Hartog, Jack A. J. den
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p. 3141 - 3151
(2007/10/02)
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