- Oxidative degradation of arylfuro-1,2-oxazoles to arylnitriles by potassium permanganate
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Arylfuroisoxazolines are oxidatively degraded to arylnitriles by treatment with a mixture of potassium permanganate and sodium acetate in dry dioxane.
- Salgado-Zamora, Hector,Campos, Elena,Jimenez, Rogelio,Ruiz, Rosalba,Castaneda, Teresa,Turijan, Sara
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- Complementary Syntheses Giving Access to a Full Suite of Differentially Substituted Phthalocyanine-Porphyrin Hybrids
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Phthalocyanines and porphyrins are often the scaffolds of choice for use in widespread applications. Synthetic advances allow bespoke derivatives to be made, tailoring their properties. The selective synthesis of unsymmetrical systems, particularly phthalocyanines, has remained a significant unmet challenge. Porphyrin-phthalocyanine hybrids offer the potential to combine the favorable features of both parent structures, but again synthetic strategies are poorly developed. Here we demonstrate strategies that give straightforward, controlled access to differentially substituted meso-aryl-tetrabenzotriazaporphyrins by reaction between an aryl-aminoisoindolene (A) initiator and a complementary phthalonitrile (B). The choice of precursors and reaction conditions allows selective preparation of 1:3 Ar-ABBB and, uniquely, 2:2 Ar-ABBA functionalized hybrids.
- Alkorbi, Faeza,Díaz-Moscoso, Alejandro,Gretton, Jacob,Chambrier, Isabelle,Tizzard, Graham J.,Coles, Simon J.,Hughes, David L.,Cammidge, Andrew N.
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- HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
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We report an efficient HCl·DMPU assisted one-pot conversion of aldehydes into nitriles. The use of HCl·DMPU as both an acidic source as well as a non-nucleophilic base constitutes an environmentally mild alternative for the preparation of nitriles. Our protocol proceeds smoothly without the use of toxic reagents and metal catalysts. Diverse functionalized aromatic, aliphatic and allylic aldehydes incorporating various functional groups were successfully converted to nitriles in excellent to quantitative yields. This protocol is characterized by a broad substrate scope, mild reaction conditions, and high scalability. This journal is
- Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
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supporting information
p. 4161 - 4164
(2020/07/14)
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- Para-Selective Cyanation of Arenes by H-Bonded Template
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The significance of site selective functionalization stands upon the superior selectivity, easy synthesis and diverse product utility. In this work, we demonstrate the para-selective introduction of versatile nitrile moiety, enabled by a detachable and reusable H-bonded auxiliary. The methodology holds its efficiency irrespective of substrate electronic bias. The conspicuous shift in the step energetics was probed by both experimental and computational mechanistic tools, which heralds the inception of para-deuteration. The synthetic impact of the methodology was highlighted with reusability of directing group and post synthetic modifications.
- Pimparkar, Sandeep,Bhattacharya, Trisha,Maji, Arun,Saha, Argha,Jayarajan, Ramasamy,Dutta, Uttam,Lu, Gang,Lupton, David W.,Maiti, Debabrata
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supporting information
p. 11558 - 11564
(2020/08/14)
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- Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
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A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
- Fang, Wan-Yin,Qin, Hua-Li
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p. 5803 - 5812
(2019/05/14)
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- An effective preparation of both 1,3-diketones and nitriles from alkynones with oximes as hydroxide sources
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An effective phosphine-catalyzed protocol has been established for the syntheses of 1,3-diketones and nitriles from alkynones with oximes as hydroxide surrogates. This method features the use of a phosphine catalyst, compatibility with various functional groups and ambient temperature, which makes this approach very practical. A plausible mechanism was proposed.
- Chen, Pei,Zhang, Qian-Qian,Guo, Jia,Chen, Lu-Lu,Wang, Yan-Bo,Zhang, Xiao
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p. 6958 - 6966
(2018/10/02)
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- Selective synthesis of benzo[4,5]imidazo[2,1-a]isoquinolines via copper-catalyzed tandem annulation of alkynylbenzonitriles with 2-Iodoanilines
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An efficient copper-catalyzed cascade cyclization reaction for selectively synthesizing a variety of benzo[4,5]imidazo[2,1-a]isoquinoline derivatives has been developed. The reaction features the formation of three different C–N bonds in sequence. In the
- Liu, Xiaodong,Deng, Guobo,Liang, Yun
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p. 2844 - 2847
(2018/06/18)
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- A radical cyclization cascade of 2-alkynylbenzonitriles with sodium arylsulfinates
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A convenient radical cyclization cascade procedure for the construction of sulfonated indenones from 2-alkynylbenzonitriles and sodium arylsulfinates has been explored under mild reaction conditions. The present methodology offers a low-cost and operationally straightforward approach to synthesizing various sulfonated indenones in moderate to good yields by simple use of cheap sodium persulfate as an oxidant and environmentally benign water as a co-solvent.
- Zhou, Bang,Chen, Wenqi,Yang, Yuzhong,Yang, Yuan,Deng, Guobo,Liang, Yun
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p. 7959 - 7963
(2018/11/21)
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- Experimental and Computational Exploration of para-Selective Silylation with a Hydrogen-Bonded Template
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The regioselective conversion of C?H bonds into C?Si bonds is extremely important owing to the natural abundance and non-toxicity of silicon. Classical silylation reactions often suffer from poor functional group compatibility, low atom economy, and insufficient regioselectivity. Herein, we disclose a template-assisted method for the regioselective para silylation of toluene derivatives. A new template was designed, and the origin of selectivity was analyzed experimentally and computationally. An interesting substrate–solvent hydrogen-bonding interaction was observed. Kinetic, spectroscopic, and computational studies shed light on the reaction mechanism. The synthetic significance of this strategy was highlighted by the generation of a precursor of a potential lipophilic bioisostere of γ-aminobutyric acid (GABA), various late-stage diversifications, and by mimicking enzymatic transformations.
- Maji, Arun,Guin, Srimanta,Feng, Sheng,Dahiya, Amit,Singh, Vikas Kumar,Liu, Peng,Maiti, Debabrata
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supporting information
p. 14903 - 14907
(2017/10/30)
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- One-pot transformation of methylarenes into aromatic nitriles with inorganic metal-free reagents
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Various methylarenes were transformed into the corresponding aromatic nitriles in good to moderate yields by the treatment with aq. HBr and aq. H 2O2, followed by reaction with molecular iodine and aq. ammonia in a one-pot procedure. The present reaction is a useful, practical, transition-metal-free, and organic-reagent-free method for the preparation of aromatic nitriles from methylarenes. Various methylarenes were treated with aq. HBr and aq. H2O2 under warming conditions and/or irradiation conditions, followed by the reaction with molecular iodine and aq. ammonia, to provide the corresponding aromatic nitriles, in a one-pot procedure. The present reaction was carried out under metal-free and organic-reagent-free conditions. Copyright
- Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
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p. 4115 - 4122
(2014/07/08)
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- Direct oxidative conversion of methylarenes into aromatic nitriles
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A variety of methylarenes were successfully converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with NBS or DBDMH in the presence of a catalytic amount of AIBN or BPO, followed by the reaction with molecular iodine in aq NH3 in a one-pot procedure. The present reaction is a useful and practical transition-metal-free method for the preparation of aromatic nitriles from methylarenes.
- Tsuchiya, Daisuke,Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
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supporting information
p. 4194 - 4197
(2013/09/12)
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- Novel syntheses of fluorenones via nitrile-directed palladium-catalyzed C-H and dual C-H bond activation
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Novel procedures for the [Pd]/[Ag]/TFA system catalyzed cascade reactions of nitrile directed remote C-H and dual C-H bond activation with insertion of nitrile were developed, which afforded variously polysubstituted fluorenones in moderate to good yields with tolerance of a wide variety of substrates.
- Wan, Jung-Chih,Huang, Jun-Min,Jhan, Yu-Huei,Hsieh, Jen-Chieh
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supporting information
p. 2742 - 2745
(2013/07/19)
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- Ruthenium-catalyzed intramolecular selective halogenation of O-methylbenzohydroximoyl halides: A new route to halogenated aromatic nitriles
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The intramolecular halogenation of O-methylbenzohydroximoyl halides in the presence of a Ru catalyst and the ligand diphenylacetylene afforded halo substituted aromatic nitriles in a highly regioselective manner. Further, substituted nitriles were converted into substituted tetrazole derivatives in the presence of NaN3 and I2.
- Chinnagolla, Ravi Kiran,Pimparkar, Sandeep,Jeganmohan, Masilamani
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supporting information
p. 3146 - 3148
(2013/06/04)
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- Concise synthesis of highly substituted benzo[a]quinolizines by a multicomponent reaction/allylation/heck reaction sequence
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The combination of the recently developed multicomponent construction of highly substituted 3,4-dihydropyridones with subsequent allylation and intramolecular Heck-type cyclization allows the straightforward construction of benzo[a]quinolizines, a class of polycyclic compounds that- despite their interesting pharmacological and photochemical properties- have little precedent in the literature. After optimization of the individual steps, we used this reliable three-step sequence to generate a small library of diversely substituted benzo[a]quinolizines and various heterocyclic analogs. Copyright
- Den Heeten, Rene,Van Der Boon, Leon J. P.,Broere, Daniel L. J.,Janssen, Elwin,De Kanter, Frans J. J.,Ruijter, Eelco,Orru, Romano V. A.
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supporting information; experimental part
p. 275 - 280
(2012/02/04)
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- Rapid synthesis and zebrafish evaluation of a phenanthridine-based small molecule library
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A Heck cyclisation approach is described for the rapid synthesis of a library of natural product-like small molecules, based on the phenanthridine core. The synthesis of a range of substituted benzylamine building blocks and their incorporation into the library is reported, together with a highly selective cis-dihydroxylation protocol that enables access to the target compounds in an efficient manner. Biological evaluation of the library using zebrafish phenotyping has led to the discovery of compound 20c, a novel inhibitor of early-stage zebrafish embryo development.
- Donaldson, Lauren R.,Wallace, Stephen,Haigh, David,Patton, E. Elizabeth,Hulme, Alison N.
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supporting information; experimental part
p. 2233 - 2239
(2011/04/27)
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- Synthesis of [1]Benzothieno[3,2-d]pyrimidines Substituted with Electron Donating Substituents on the Benzene Ring
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Various 2-fluorobenzonitriles were converted to the corresponding 3-amino[1]benzothiophenecarboxylic acid esters, which in turn were annulated with formamidine or various equivalents to produce the desired tricyclic benzothienopyrimidines. Various methoxy and nitro/amino substituants were placed on the phenyl ring, requiring several different strategies to prepare the desired benzothiophenes. Several different pyrimidone annulations were also required. The use of an electron rich 2-bromobenzonitrile in a four-step one-pot low temperature lithiation sequence to produce highly electron-rich amino[1]benzothiophenecarboxylate esters is also described. The synthesis of 7-amino-8-fluoro[1]benzothieno[3,2-d]pyrimid-4(3H)-one was relatively straightforward, but synthesis of the corresponding 7-amino-8-protio analogue proved to be very difficult, and required several approaches before a successful one was found.
- Bridges, Alexander J.,Zhou, Hairong
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p. 1163 - 1172
(2007/10/03)
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