635683-12-4Relevant articles and documents
Iron-catalyzed reductive strecker reaction
Yan, Fachao,Huang, Zijun,Du, Chen-Xia,Bai, Jian-Fei,Li, Yuehui
, p. 188 - 194 (2021/02/03)
Strecker reaction is widely applied for the synthesis of amino acids from aldehydes, amines and cyanides. Herein, we report the FeI2-catalyzed reductive Strecker type reaction of formamides instead of aldehydes to produce amino acetonitriles. The challenging capture of carbinolamine intermediates by CN? was achieved via Fe catalysis. This approach afforded better yields than the use of Ir- or Rh-catalysts. The application ability of this methodology is demonstrated by 1) one-pot construction of (13C labeled) complex molecules from CO2 via amino acetonitrile intermediates and 2) convenient production of homologated carboxylic acids from aldehydes.
Iron-Catalyzed α-C-H Cyanation of Simple and Complex Tertiary Amines
Yilmaz, Ozgur,Dengiz, Cagatay,Emmert, Marion H.
supporting information, p. 2489 - 2498 (2021/02/06)
This manuscript details the development of a general and mild protocol for the α-C-H cyanation of tertiary amines and its application in late-stage functionalization. Suitable substrates include tertiary aliphatic, benzylic, and aniline-type substrates and complex substrates. Functional groups tolerated under the reaction conditions include various heterocycles and ketones, amides, olefins, and alkynes. This broad substrate scope is remarkable, as comparable reaction protocols for α-C-H cyanation frequently occur via free radical mechanisms and are thus fundamentally limited in their functional group tolerance. In contrast, the presented catalyst system tolerates functional groups that typically react with free radicals, suggesting an alternative reaction pathway. All components of the described catalyst system are readily available, allowing implementation of the presented methodology without the need for lengthy catalyst synthesis.
Nano cobalt-copper ferrite catalyzed regioselective α-C(sp3)–H cyanation of amines: Secondary, tertiary, and drug molecules
Heidarian, Mahdi,Moghaddam, Firouz Matloubi,Pourkaveh, Raheleh
, (2020/11/03)
Oxidative cyanation of sp3C–H bonds at the α position of amines was achieved using CoCuFe2O4 as a catalyst and NaCN as an inexpensive cyanide source at room temperature. CoCuFe2O4 was found to be an active catalyst for Csp [3]-Csp coupling, efficiently delivering valuable α-aminonitriles from tertiary/secondary amines in good yields. The corresponding products were obtained with high selectivity toward α position. In addition, functional group tolerance offered the opportunity for application in late-stage functionalization of biologically active molecules. This transformation proceeds convenient on a gram-scale, and the catalyst can be reused for several runs with consistent catalytic activity.
Method for preparing alpha-aminonitrile and product and application thereof
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Paragraph 0061-0065, (2021/02/24)
The invention discloses a method for preparing alpha-aminonitrile, which comprises the following steps: by using tertiary amine and benzoyl cyanide as reactants, carrying out visible light irradiationin an organic solvent under the condition of oxygen or
Electron Donor-Acceptor Complex-Initiated Photochemical Cyanation for the Preparation of α-Amino Nitriles
Xia, Qing,Li, Yufei,Cheng, Lan,Liang, Xin,Cao, Chenlin,Dai, Peng,Deng, Hongping,Zhang, Weihua,Wang, Qingmin
supporting information, p. 9638 - 9643 (2020/12/21)
An electron donor-acceptor complex-initiated α-cyanation of tertiary amines has been described. The reaction protocol provides a novel method to synthesize various α-amino nitriles under mild conditions. The reaction can proceed smoothly without the presence of photocatalysts and transition metal catalysts, and either oxidants are unnecessary or O2 is the only oxidant. The practicality of this method is showcased not only by the late-stage functionalization of natural alkaloid derivatives and pharmaceutical intermediate, but also by the applicability of a stop-flow microtubing reactor.
Covalently hooked EOSIN-Y in a Zr(IV) framework as visible-light mediated, heterogeneous photocatalyst for efficient C–H functionalization of tertiary amines
Kumar, Gaurav,Solanki, Pratik,Nazish, Mohd,Neogi, Subhadip,Kureshy, Rukhsana I.,Khan, Noor-ul H.
, p. 298 - 304 (2019/02/26)
Herein, we report the synthesis of a novel heterogeneous photo-catalyst by utilizing post-synthetic modification of an amine functionalized Zr(IV) metal-organic framework (UiO-66-NH2) through covalent hooking of EOSIN-Y via dehydrating coupling. The characterization of the catalyst was accomplished by FT-IR, XRD, BET surface analysis, TGA, as well as TEM, SEM, XPS, DRS-UV–visible, and NMR spectroscopy, confirming successful covalent linking of EOSIN-Y with the pendent –NH2 functionality in the framework. That post-modified EY@UiO-66-NH2 acts as simple and green visible light mediated photo-catalyst for the C–H activation of tertiary amines with excellent yields. Importantly, the activity of dye incorporated heterogeneous photo-catalyst is found superior to that for the homogeneous photo-catalyst EOSIN-Y. Thus, separation difficulty of homogeneous catalysis, as well as the environmental adverse effects of toxic EOSIN-Y can be excluded by developing such photo-catalyst. Moreover, EY@UiO-66-NH2 catalyst could be consistently recycled up to 10 cycles, without any significant loss in activity. Based on literature report and experimental findings, we also propose a plausible mechanism for the reaction.
New catalytic effect of thiourea on the oxidative cyanation of N-aryltetrahydroisoquinolines
Ullah, Bakhtar,Zhou, Yuli,Chen, Jingwen,Bao, Zongbi,Yang, Yiwen,Yang, Qiwei,Ren, Qilong,Zhang, Zhiguo
supporting information, p. 348 - 351 (2019/01/04)
Thiourea itself has been introduced as a mild and efficient organocatalyst for the oxidative α -cyanation of N-aryltetrahydroisoquinolines (THIQs) with trimethylsilyl cyanide (TMSCN), giving the corresponding products in good to excellent yields. Experime
Iron-catalysed carbene-transfer reactions of diazo acetonitrile
Empel, Claire,Hock, Katharina J.,Koenigs, Rene M.
supporting information, p. 7129 - 7133 (2018/10/24)
A continuous-flow protocol for the synthesis of diazo acetonitrile was developed. It was further applied in iron-catalysed insertion reactions of diazo acetonitrile into N-H and S-H bonds to yield valuable α-substituted acetonitrile, including gram-scale synthesis.
A highly efficient heterogeneous ruthenium-catalysed oxidative α-cyanation of tertiary amines leading to α-aminonitriles
Wang, Xiaoming,Xiao, Ruian,Ai, Jingting,Cai, Mingzhong
, p. 576 - 580 (2017/11/14)
Oxidative α-cyanation of tertiary amines was achieved by using an MCM-41-immobilised N-alkylethylenediamine ruthenium(III) complex (MCM-41-2N-RuCl3) as catalyst in MeOH at 60 oC in the presence of H2O2 as oxidant and NaCN
Metal-Free Aerobic Oxidative Cyanation of Tertiary Amines: Azobis(isobutyronitrile) (AIBN) as a Sole Cyanide Source
Liu, Peng-Yu,Zhang, Chao,Zhao, Shi-Chen,Yu, Fang,Li, Fei,He, Yu-Peng
, p. 12786 - 12790 (2017/12/08)
An aerobic oxidative cyanation for the synthesis of α-aminonitriles was reported. The formation of C(sp3)-CN bonds was achieved under a metal-free condition by utilizing azobis(isobutyronitrile) as a sole organic cyanide source with the combination of pivalic acid and sodium acetate as additives.
