- Isocyanide 2.0
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The isocyanide functionality due to its dichotomy between carbenoid and triple bond characters, with a nucleophilic and electrophilic terminal carbon, exhibits unusual reactivity in organic chemistry exemplified for example in the Ugi reaction. Unfortunately, the over proportional use of only a few isocyanides hampers novel discoveries about the fascinating reactivity of this functional group. The synthesis of a broad range of isocyanides with multiple functional groups is lengthy, inefficient, and exposes the chemist to hazardous fumes. Here we present an innovative isocyanide synthesis overcoming these problems by avoiding the aqueous workup which we exemplify by parallel synthesis from a 0.2 mmol scale performed in 96-well microtiter plates up to a 0.5 mol multigram scale. The advantages of our methodology include an increased synthesis speed, very mild conditions giving access to hitherto unknown or highly reactive classes of isocyanides, rapid access to large numbers of functionalized isocyanides, increased yields, high purity, proven scalability over 5 orders of magnitude, increased safety and less reaction waste resulting in a highly reduced environmental footprint. For example, the hitherto believed to be unstable 2-isocyanopyrimidine, 2-acylphenylisocyanides and even o-isocyanobenzaldehyde could be accessed on a preparative scale and their chemistry was explored. Our new isocyanide synthesis will enable easy access to uncharted isocyanide space and will result in many discoveries about the unusual reactivity of this functional group. This journal is
- Ahmadian-Moghaddam, Maryam,D?mling, Alexander,Patil, Pravin
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supporting information
p. 6902 - 6911
(2020/11/09)
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- Visible-light-induced radical cascade cyclization of oxime esters and aryl isonitriles: Synthesis of cyclopenta[: B] quinoxalines
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A visible-light-induced radical cascade cyclization of aryl isonitriles and cyclobutanone oxime esters for the synthesis of cyclopenta[b]quinoxalines has been accomplished for the first time. The key to the success of this process was the integration of the in situ-formed nitrile radical followed by the cascade radical isonitrile/nitrile insertion-cyclization. The easy introduction of substituents for both substrates and the high functional group tolerance of the reaction make it an efficient strategy to give various quinoxaline derivatives in moderate to good yields.
- Yuan, Yao,Dong, Wu-Heng,Gao, Xiao-Shuang,Xie, Xiao-Min,Zhang, Zhao-Guo
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p. 11900 - 11903
(2019/10/11)
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- Selective Gold-Catalysed Synthesis of Cyanamides and 1-Substituted 1H-Tetrazol-5-Amines from Isocyanides
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The newly discovered gold-catalysed reaction of isocyanides with hydrazoic acid generated in situ from trimethylsilyl azide and methanol (or, alternatively, from NaN3/AcOH) produces either cyanamides or 1-substituted 1H-tetrazol-5-amines, depending on the amount of available HN3. The reaction proceeds selectively and in generally high yields of either product, thus providing a particularly convenient access to a wide range of substituted 1H-tetrazol-5-amines that are rather difficult to access otherwise.
- ?koch, Karel,Císa?ová, Ivana,?těpni?ka, Petr
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p. 13788 - 13791
(2018/09/14)
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- Visible-Light-Induced Radical Cascade Cyclization: Synthesis of the ABCD Ring Cores of Camptothecins
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A new strategy for constructing indolizino[1,2-b]quinolin-9(11H)-ones (ring cores of camptothecins) from readily available isocyanoarenes and N-(alkyl-2-yn-1-yl)pyridin-2(1H)-ones has been developed through a visible-light-induced radical cascade cyclization process. The reaction proceeds under mild conditions with fair to excellent yields. The easy introduction of substituents for both reactants and the broad functional group tolerance of the reaction make it a straightforward route to the cores of the marketed camptothecins and their derivatives.
- Yuan, Yao,Dong, Wuheng,Gao, Xiaoshuang,Gao, Huang,Xie, Xiaomin,Zhang, Zhaoguo
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p. 2840 - 2846
(2018/03/09)
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- Silver-Catalyzed Chemoselective [4+2] Annulation of Two Isocyanides: A General Route to Pyridone-Fused Carbo- and Heterocycles
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A silver-catalyzed chemoselective [4+2] annulation of aryl and heteroaryl isocyanides with α-substituted isocyanoacetamides was developed for the facile and efficient synthesis of 2-aminoquinolones, naphthyridines, and phenanthrolines. A mechanism for this multistep domino reaction is proposed on the basis of a13C-labeling experiment, according to which an unprecedented chemoselective heterodimerization of two different isocyanides generates an α-amidoketenimine intermediate, which undergoes 1,3-amino migration to form an α-imidoylketene, followed by 6 π electrocyclization.
- Hu, Zhongyan,Dong, Jinhuan,Men, Yang,Lin, Zhichen,Cai, Jinxiong,Xu, Xianxiu
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supporting information
p. 1805 - 1809
(2017/02/05)
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- Cobalt(II)-Catalyzed Isocyanide Insertion Reaction with Sulfonyl Azides in Alcohols: Synthesis of Sulfonyl Isoureas
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A Co(II)-catalyzed isocyanide insertion reaction with sulfonyl azides in alcohols to form sulfonyl isoureas via nitrene intermediate has been developed. This protocol provides a new, environmentally friendly, and simple strategy for the synthesis of sulfonyl isourea derivatives by employing a range of substrates under mild conditions.
- Jiang, Tian,Gu, Zheng-Yang,Yin, Ling,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 7913 - 7919
(2017/08/14)
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- Synthesis of selenazolopyridine derivatives with capability to induce apoptosis in human breast carcinoma MCF-7 cells through scavenge of intracellular ROS
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A series of selenazolopyridine derivatives have been synthesized and characterized by X-ray diffraction, high resolution NMR and Mass spectrum. The in vitro anticancer activities of the synthetic compounds were screened against a panel of human cancer cell lines, human breast carcinoma MCF-7 cells, human liver carcinoma HepG2 cells and L02 normal cell line by MTT assay. By analyzing the structure-activity relationship among the synthetic compounds, it was found that 2-(phenylamino) selenazolo [5,4-b] pyridine, (PSeD, 7) had higher growth inhibitory effect on MCF-7 cells. The intracellular mechanism of cell death was evaluated by flow cytometric analysis and ROS assay, which revealed that PSeD could induce MCF-7 cells apoptosis by scavenging intracellular ROS. Taken together, we regard PSeD as an antioxidant which could inhibit cancer cell growth through induction of apoptosis.
- Zhou, Meiyun,Ji, Shengbin,Wu, Zhaojun,Li, Yiqun,Zheng, Wenjie,Zhou, Hua,Chen, Tianfeng
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- Synthesis of isocyanides through dehydration of formamides using XtalFluor-E
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The formation of isocyanides from formamides using XtalFluor-E, [Et2NSF2]BF4, is presented. A wide range of formamides can be used to produce the corresponding isocyanides in up to 99% yield. In a number of cases, the crude products showed good purity (generally >80% by NMR) allowing to be used directly in multi-component reactions.
- Keita, Massaba,Vandamme, Mathilde,Mahé, Olivier,Paquin, Jean-Fran?ois
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supporting information
p. 461 - 464
(2015/03/05)
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- Synthesis of sugar-derived isoselenocyanates, selenoureas, and selenazoles
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Aryl, alkyl, and sugar-derived isoselenocyanates were prepared by a one-pot procedure starting from the corresponding formamides, using triphosgene as a dehydrating agent, triethylamine, and black selenium powder. The preparation of sugar selenoureas by coupling of O-protected sugar-derived isoselenocyanates with different amines, and by coupling of unprotected glycopyranosyl amines with phenyl isoselenocyanate was also accomplished. The synthesis of a glucopyranos-2-yl-selenazole starting from O-protected 2-amino-2-deoxy-d-glucose by coupling with benzoyl isoselenocyanate, Se-alkylation with phenacyl bromide, and acid-catalyzed dehydration is also reported. Unprotected N-(β-d-glucopyranosyl)-N′-phenylselenourea was transformed into a 1,2-trans-fused bicyclic isourea upon treatment with aqueous hydrogen peroxide; the same isourea was prepared by a one-pot three-step procedure from β-d-glycopyranosylamine by thiophosgenation, coupling with aniline, and HgO-mediated desulfurization.
- López, óscar,Maza, Susana,Ulgar, Víctor,Maya, Inés,Fernández-Bola?os, José G.
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experimental part
p. 2556 - 2566
(2009/08/08)
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- Isonitrile trapping reactions under thermolysis of alkoxyamines for the synthesis of quinolines
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An efficient tandem radical process comprising a thermal alkoxyamine homolysis, an isonitrile trapping reaction, a 5-exo-trig cyclization, and a homolytic aromatic substitution leads to substituted dihydroquinolines. Depending on the substituent R1, oxidation to dihydro-1H-cyclopenta- [b]quinolines (for R1 = aryl) or tautomerization to tetrahydro-1H-cyclopenta[b]quinolines (for R1 = CO2Me, CN) occurs. The heterocycles are obtained in moderate to good yields. Upon using microwave-induced heating, the reaction time can be shortened from 3 days to 30 min.
- Janza, Birgit,Studer, Armido
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p. 1875 - 1878
(2007/10/03)
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- METHOD FOR PRODUCING NITRILES AND ISONITRILES BY USING DEHYDRATION REACTORS WITH PROPANEPHOSPHONIC ACID ANHYDRIDES
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The invention concerns a method for producing: a) nitriles of formula (II) and; b) isonitriles of formula (III) by reacting: a) carboxylic acid amides (RCO-NH2), ammonium salts of carboxylic acids (RCOO-NH4+) or carboxylic acids in the presence of ammonia or ammonium salts (RCOOH +NH3, RCOOH + NH4+) or; b) formamides (H-CO-NHR) or mixtures of amines with formic acid, with cyclic phosphonic acid anhydrides while eliminating water at a temperature ranging from -30 to +120 °C, in which R represents an arbitrarily substituted linear or branched C1-C8 alkyl radical, a C3-C10 cycloalkyl radical, alkenyl radical, alkynyl radical or an aryl radical or heteroaryl radical. As a cyclic phosphonic acid anhydride, a 2,4,6,-substituted 1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide of formula (I) is used, in which: x = 3, 4 or 5; R', independent of one another, represents open-chain or branched, saturated or unsaturated, straight-chain C1 to C16 alkyl radicals or cyclic C3 to C16 alkyl radicals or aryl or heteroaryl.
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Page/Page column 7
(2008/06/13)
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- iron(II) Compounds with Isocyanides as Axial Ligands
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Aliphatic and aromatic monodentate isocyanides RNC (R = t-Bu, c-Hx, substituted Ph) react with iron(II) (TPyPFe) to form the corresponding diaxially substituted iron(II) compounds TPyPFe(RNC)2 1a-8a.The spectroscopic data and thermal properties of the complexes are described and compared with the analogous PcFe(CNR)2 compounds 1b-8b.
- Hanack, Michael,Thies, Ruediger
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p. 1225 - 1230
(2007/10/02)
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- DI-2-PYRIDYL SULFITE. A NEW USEFUL REAGENT FOR THE PREPARATION OF N-SULFINYLAMINES, NITRILES, ISOCYANIDES, AND CARBODIIMIDES UNDER MILD CONDITIONS
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Di-2-pyridyl sulfite is a very useful reagent for the preparation of N-sulfinylamines, nitriles, isocyanides, and carbodiimides in high yields under essentially neutral conditions.
- Kim, Sunggak,Yi, Kyu Yang
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p. 1925 - 1928
(2007/10/02)
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