- 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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- TEMPO-Catalyzed Aerobic Oxidative Selenium Insertion Reaction: Synthesis of 3-Selenylindole Derivatives by Multicomponent Reaction of Isocyanides, Selenium Powder, Amines, and Indoles under Transition-Metal-Free Conditions
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A novel and efficient approach for the selenium functionalization of indoles was developed with selenium powder as the selenium source, catalyzed by 2,2,6,6-tetramethylpiperidinooxy (TEMPO) and employing O2 as the green oxidant. This protocol provides a practical route for the synthesis of 3-selenylindole derivatives and has the advantages of readily available starting materials, mild reaction conditions, and a wide scope of substrates. Electron spin-resonance (ESR) studies reveal that the approach involves the formation of nitrogen-centered radicals and selenium radicals via oxidation of in situ generated selenoates.
- Liu, Huan,Fang, Yi,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 930 - 933
(2018/02/22)
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- Aerobic radical-cascade cycloaddition of isocyanides, selenium and imidamides: Facile access to 1,2,4-selenadiazoles under metal-free conditions
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A novel and facile metal-free method for the green synthesis of 1,2,4-selenadiazol-5-amine derivatives through the aerobic radical-cascade multi-component reactions of isocyanides, selenium powder and imidamides is reported herein. O2 in the air was employed as the green oxidant to achieve the cycloaddition with the generation of H2O as the sole by-product. It also features good functional group compatibility and broad substrate scope. In addition, this method was successfully applied to the functionalization of biologically active molecules.
- Fang, Yi,Zhu, Zheng-Lin,Xu, Pei,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 1613 - 1618
(2017/06/05)
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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 Isoselenocyanates
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Isoselenocyanates were synthesized by two methods under phase-transfer conditions (50% aq NaOH, CH2Cl2, Aliquat 336); the first started from isocyanides and selenium and gave isoselenocyanates in 61-89% yields, while the second started from amines and used chloroform and selenium, by applying sequentially the Hofmann isonitrile synthesis and the addition of selenium, in 4-70% yields.
- Zakrzewski, Jerzy,Huras, Bogumi?a,Kie?czewska, Anna
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- CHEMICAL COMPOUNDS
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This invention relates to non-steroidal compounds that are modulators of androgen receptor, and also to the methods for the making and use of such compounds.
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Page/Page column 35; 37
(2008/12/04)
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- Microwave-assisted synthesis of isonitriles: A general simple methodology
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(Chemical Equation Presented) A facile conversion of formamides to isonitriles under very mild conditions and microwave irradiation is described. This simple and efficient method has been applied for the synthesis of both aliphatic and aromatic isonitriles in high yields.
- Porcheddu, Andrea,Giacomelli, Giampaolo,Salaris, Margherita
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p. 2361 - 2363
(2007/10/03)
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- Living polymerization of butadiene at both chain ends via a bimetallic nickel initiator. Preparation of hydroxytelechelic poly(butadiene) and symmetric poly(isocyanide-b-butadiene-b-isocyanide) elastomeric triblock copolymers
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A bifunctional nickel initiator, bis(μ-trifluoroacetato)(η3:η 3-2,2′-biallyl)dinickel(II), IV, was synthesized to promote the living polymerization of butadiene to high cis-1,4-content polymer with both chain ends active. Other potential initiators, [1,4-phenylenebis((η3-1-allyl)nickeltrifluoroacetate)] n),II, and[1,4-cyclohexanediylbis((η3-1-allyl)-nickel trifluoroacetate)]n, III, were found to be completely ineffective due to intermolecular carboxylate bridges which gave the complexes polymeric structures. The intramolecular bridges in IV and its molecularity were confirmed by X-ray crystallography. IV cocrystallizes in space group P1 with 0.5 equiv of 2,3-bis((trifluoroacetoxy)methyl)-1,3-butadiene in the unit cell with constants of a = 9.5600(8) A?, b = 9.6554(9) A?, c = 11.7615(10) A?; α = 73.711(7)?, β = 73.537(7)?, γ = 71.938(7)?; V=967.50(15) A?3; and Z=2. Refinement of the model, which contained a disordered C6H8 unit, led to convergence with Rf = 5.8%, RwF = 6.9%, and GOF = 2.21 for 276 variables refined against those 2852 data with |F?|>3.0σ/(|F?|)). The living polybutadiene samples were successfully used to prepare triblock copolymers of the structure poly (1-phenylethyl isocyanide-b-butadiene-b-1-phenylethyl isocyanide), which have been characterized using gel permeation chromatography, differential scanning calorimetry, 13C NMR, elemental analysis, and transmission electron microscopy. The bifunctional living polybutadiene was also successfully end-capped with p-(trifluoromethyl)-benzaldehyde to afford a telechelic polymer with hydroxy functionalities at both chain ends.
- Deming, Timothy J.,Novak, Bruce M.,Ziller, Joseph W.
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p. 2366 - 2374
(2007/10/02)
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