41010-09-7Relevant academic research and scientific papers
Polyoxotungstate Photoinduced Alkylation of Electrophilic Alkenes by Cycloalkanes
Dondi, Daniele,Fagnoni, Maurizio,Molinari, Alessandra,Maldotti, Andrea,Albini, Angelo
, p. 142 - 148 (2004)
Alkyl radical obtained by irradiation of tetrabutylammonium decatungstate in acetonitrile in the presence of cycloalkanes (C5H10, C6H12, C7H14) are efficiently trapped by electrophilic alkenes (acrylonitrile, isopropylydenmalonitrile, isopropylydencyanoacetate) to give the corresponding alkylated aliphatic nitriles. The reaction can be carried out up to complete conversion of the alkene with reasonable (in most cases 60-65%) yields. Addition of the radicals to the alkene is followed by electron transfer from reduced decatungstate regenerating the sensitizer (turn over number up to 60). Steady-state measurements, EPR evidence, deuteration experiments and attempted intramolecular trapping of the adduct radical support the mechanistic proposal.
Development of an Operationally Simple, Scalable, and HCN-Free Transfer Hydrocyanation Protocol Using an Air-Stable Nickel Precatalyst
Reisenbauer, Julia C.,Bhawal, Benjamin N.,Jelmini, Nicola,Morandi, Bill
supporting information, p. 1165 - 1173 (2022/03/01)
Hydrocyanation reactions enable access to synthetically valuable nitriles from readily available alkene precursors. However, hydrocyanation reactions using hydrogen cyanide (HCN) or similarly toxic reagents on laboratory scale can be particularly challenging due to their hazardous nature. In addition, such processes typically require air- and temperature-sensitive Ni(0) precatalysts, further reducing the operational simplicity of this transformation. Herein, we report a HCN-free transfer hydrocyanation of alkenes and alkynes that employs commercially available aliphatic nitriles as sacrificial HCN donors in combination with a catalytic amount of air-stable and inexpensive NiCl2as a precatalyst and a cocatalytic Lewis acid. The scalability and robustness of the catalytic process were demonstrated by the hydrocyanation of α-methylstyrene on a 100 mmol scale (11.4 g of product obtained) using 1 mol % of the Ni catalyst. In addition, the feasibility of the dehydrocyanation protocol using the air-stable Ni(II) precatalyst and norbornadiene as a sacrificial acceptor was showcased by the selective conversion of an aliphatic nitrile into the corresponding alkene.
A Titanium-Catalyzed Reductive α-Desulfonylation
Kern, Christoph,Selau, Jan,Streuff, Jan
supporting information, p. 6178 - 6182 (2021/03/16)
A titanium(III)-catalyzed desulfonylation gives access to functionalized alkyl nitrile building blocks from α-sulfonyl nitriles, circumventing traditional base-mediated α-alkylation conditions and strong single electron donors. The reaction tolerates numerous functional groups including free alcohols, esters, amides, and it can be applied also to the α-desulfonylation of ketones. In addition, a one-pot desulfonylative alkylation is demonstrated. Preliminary mechanistic studies indicate a catalyst-dependent mechanism involving a homolytic C?S cleavage.
Preparation method of alkyl nitrile compound
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Paragraph 0214-0216; 0235-0237; 0244-0246, (2020/08/18)
The invention discloses a preparation method of an alkyl nitrile compound. Specifically, the preparation method comprises the following step: in an organic solvent, in the presence of a protective gasand under the action of a catalyst, carrying out a reduction reaction as shown in the specification on olefin as shown in a formula I, a cyanation reagent and water, wherein the alkyl nitrile compound 1 is a compound II and/or a compound III. The preparation method provided by the invention is mild in condition, can realize hydrocyanation of olefin more safely and efficiently, and has good substrate universality and functional group compatibility.
Catalyst-Free Decarboxylation of Carboxylic Acids and Deoxygenation of Alcohols by Electro-Induced Radical Formation
Chen, Xiaoping,Luo, Xiaosheng,Peng, Xiao,Guo, Jiaojiao,Zai, Jiantao,Wang, Ping
supporting information, p. 3226 - 3230 (2020/02/27)
Electro-induced reduction of redox active esters and N-phthalimidoyl oxalates derived from naturally abundant carboxylic acids and alcohols provides a sustainable and inexpensive approach to radical formation via undivided electrochemical cells. The resulting radicals are trapped by an electron-poor olefin or hydrogen atom source to furnish the Giese reaction or reductive decarboxylation products, respectively. A broad range of carboxylic acid (1°, 2°, and 3°) and alcohol (2° and 3°) derivatives are applicable in this catalyst-free reaction, which tolerated a diverse range of functional groups. This method features simple operation, is a sustainable platform, and has broad application.
Titanium(III)-Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non-Free-Radical Mechanism
Weweler, Jens,Younas, Sara L.,Streuff, Jan
, p. 17700 - 17703 (2019/11/13)
A titanium-catalyzed mono-decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. A corresponding desulfonylation is demonstrated as well. Mechanistic experiments support a catalyst-controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations. The involvement of two TiIII species in the C?C cleavage is proposed, and the beneficial role of added ZnCl2 and 2,4,6-collidine hydrochloride is investigated.
Photoinduced 1,2-Hydro(cyanomethylation) of Alkenes with a Cyanomethylphosphonium Ylide
Miura, Tomoya,Moriyama, Daisuke,Funakoshi, Yuuta,Murakami, Masahiro
supporting information, p. 511 - 514 (2019/02/26)
An efficient method has been developed for the 1,2-hydro(cyanomethylation) of alkenes, in which a cyanomethyl radical species is generated from a cyanomethylphosphonium ylide by irradiation with visible light in the presence of an iridium complex, a thiol, and ascorbic acid. The cyanomethyl radical species then adds across the C=C double bond of an alkene to form an elongated alkyl radical species that accepts a hydrogen atom from the thiol to produce an elongated aliphatic nitrile. The ascorbic acid acts as the reductant to complete the catalytic cycle.
Synthesis of Nitriles from Aldehydes with Elongation of the Molecule with Two Carbon Atoms
Afanasyev, Oleg I.,Zarochintsev, Alexander,Petrushina, Tatiana,Cherkasova, Anastasia,Denisov, Gleb,Cherkashchenko, Ilia,Chusova, Olga,Jinho, Oh,Man-Seog, Chun,Usanov, Dmitry L.,Semenov, Sergei E.,Chusov, Denis
supporting information, p. 32 - 35 (2018/12/05)
A new protocol for the synthesis of nitriles from carbonyl compounds with elongation of the molecule with two carbon atoms was developed. It involves a reaction of ethyl cyanoacetate with different aldehydes in the presence of iron pentacarbonyl as a redu
A strategy for generating aryl radicals from arylborates through organic photoredox catalysis: Photo-Meerwein type arylation of electron-deficient alkenes
Iwata,Tanaka,Kubosaki,Morita,Yoshimi
supporting information, p. 1257 - 1260 (2018/02/09)
Photoinduced reactions of arylboronic acids with electron deficient alkenes under mild organic photoredox catalysis conditions lead to the formation of Meerwein arylation type adducts via the generation of aryl radicals.
Continuous Flow Synthesis under High-Temperature/High-Pressure Conditions Using a Resistively Heated Flow Reactor
Adeyemi, Ahmed,Bergman, Joakim,Br?nalt, Jonas,S?vmarker, Jonas,Larhed, Mats
supporting information, p. 947 - 955 (2017/07/26)
A cheap, easy-to-build, and effective resistively heated reactor for continuous flow synthesis at high temperature and pressure is herein presented. The reactor is rapidly heated directly using an electric current and is capable of rapidly delivering temperatures and pressures up to 400 °C and 200 bar, respectively. High-temperature and high-pressure applications of this reactor were safely performed and demonstrated by selected transformations such as esterifications, transesterifications, and direct carboxylic acid to nitrile reactions using supercritical ethanol, methanol, and acetonitrile. Reaction temperatures were between 300 and 400 °C with excellent conversions and good to excellent isolated product yields. Examples of Diels-Alder reactions were also carried out at temperatures up to 300 °C in high yield. No additives or catalysts were used in the reactions.
