- Electrochemically promoted oxidative α-cyanation of tertiary and secondary amines using cheap AIBN
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The electrochemical α-cyanation of tertiary and secondary amines has been developed by using a cheap cyanide reagent, azobisisobutyronitrile (AIBN). The CN radical, generated throughn-Bu4NBr-meidated electrochemical oxidation, participates in a novel α-cyanation reaction under exogenous oxidant-free conditions.
- Cai, Tian-Cheng,Gui, Qing-Wen,Hu, Wenxia,Li, Qiang,Liu, Xiaoying,Teng, Fan,Wang, Xiaoli,Xiong, Zhi-Yuan,Yu, Jialing
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supporting information
p. 8254 - 8258
(2021/10/12)
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- Visible light promoted photoredox C(sp3)-H bond functionalization of tetrahydroisoquinolines in flow
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A merger of organocatalysis and visible light photoredox catalysis performed in flow allowed access to a wide range of functionalizedN-aryl-substituted tetrahydroisoquinolines (THIQs) in a formal C-H oxidation/Mannich reaction. Strecker type functionaliza
- Filipovi?, Ana,D?ambaski, Zdravko,Vasiljevi?-Radovi?, Dana,Bond?i?, Bojan P.
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supporting information
p. 2668 - 2675
(2021/04/07)
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- Cyanine-based near infra-red organic photoredox catalysis
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Direct metal-free near infra-red photoredox catalysis is applied to organic oxidation, photosensitization and reduction, involving cyanines as photocatalysts. This photocatalyst is competitive with conventional reactions catalyzed under visible light. Kin
- Baralle, Alexandre,Cormier, Morgan,Goddard, Jean-Philippe,Obah Kosso, Anne Roly,Sellet, Nicolas
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p. 6964 - 6968
(2021/06/02)
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- Donor-acceptor type [4+3] covalent organic frameworks: sub-stoichiometric synthesis and photocatalytic application
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Three unprecedented 2D [4+3] covalent organic frameworks (TTCOF-1, TTCOF-2, and TTCOF-3) have been prepared by substoichiometric condensation of tetratopic and tritopic monomers, overcoming the limitations of the design rules of conventional topologies. By reticulating the tetraphenylethylene (TPE)-based and triazine-based moieties into COF frameworks, novel electron donor-acceptor (D-A) type structures were obtained. These TTCOFs have good photocatalytic activity in aerobic C(sp3)-H bond functionalization and arylboronic acid oxidation driven by visible light, with yields up to 94%. This can expedite possibilities of COFs with new structural and topological complexities and can also expand the application of COF-based photocatalysis in synthetic chemistry.
- Liao, Qiaobo,Xu, Wentao,Huang, Xin,Ke, Can,Zhang, Qi,Xi, Kai,Xie, Jin
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p. 707 - 714
(2020/04/15)
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- Photo-induced sp3 C?H bond arylation, cyanation and nitroalkylation of tetrahydroisoquinolines (THIQs) under visible light irradiation using a combination of NHPI and Rose Bengal
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This work reports a sustainable protocol for α-arylation of tetrahydroisoquinolines (THIQs) with aryl diazonium salts using a combination of a cheap and stable oxidant, N-hydroxyphthalimide (NHPI), and an inexpensive dye photosensitizer, Rose Bengal (RB),
- Patil, Mahendra R.,Shah, Jagrut,Kumar, A. Vijay,Kapdi, Anant R.
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supporting information
p. 4302 - 4306
(2020/11/30)
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- PIFA-Promoted, Solvent-Controlled Selective Functionalization of C(sp2)-H or C(sp3)-H: Nitration via C-N Bond Cleavage of CH3NO2, Cyanation, or Oxygenation in Water
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A novel nitration (via C(sp3)-N breaking/C(sp2)-N formation with CH3NO2) mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA) is described. The NO2 transfer from CH3NO2 to the aromatic group of the substrate is possible with careful selection of the solvent, NaX, and oxidant. In addition, the solvent-controlled C(sp2)-H functionalization can shift to an α-C(sp3)-H functionalization (cyanation or oxygenation) of the α-C(sp3)-H of cyclic amines.
- Mudithanapelli, Chandrashekar,Dhorma, Lama Prema,Kim, Mi-Hyun
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- Magnetic nanoparticle-supported eosin Y ammonium salt: An efficient heterogeneous catalyst for visible light oxidative C–C and C–P bond formation
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A highly efficient visible light mediated C–C and C–P coupling reactions of sp3 C–H bonds adjacent to the nitrogen atom in tetrahydroisoquinoline derivatives with pronucleophiles such as nitroalkanes, malononitrile, dimethyl malonate and H-phos
- Li, Pinhua,Wang, Guan-Wu,Zhu, Xianjin,Wang, Lei
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supporting information
p. 3448 - 3455
(2019/05/15)
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- Covalently hooked EOSIN-Y in a Zr(IV) framework as visible-light mediated, heterogeneous photocatalyst for efficient C–H functionalization of tertiary amines
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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.
- Kumar, Gaurav,Solanki, Pratik,Nazish, Mohd,Neogi, Subhadip,Kureshy, Rukhsana I.,Khan, Noor-ul H.
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p. 298 - 304
(2019/02/26)
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- New catalytic effect of thiourea on the oxidative cyanation of N-aryltetrahydroisoquinolines
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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
- Ullah, Bakhtar,Zhou, Yuli,Chen, Jingwen,Bao, Zongbi,Yang, Yiwen,Yang, Qiwei,Ren, Qilong,Zhang, Zhiguo
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supporting information
p. 348 - 351
(2019/01/04)
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- Redox-neutral C–H cyanation of tetrahydroisoquinolines under photoredox catalysis
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Redox-neutral cyanation of C–H bond adjacent to a nitrogen atom was achieved by using the combination of a photoredox catalyst and p-toluenesulfonyl cyanide. The reaction of tetrahydroisoquinolines proceeded smoothly, affording the corresponding cyanated products selectively in good to high yield. Although the reaction rate became slower in the case of the substrates having electron-withdrawing groups, high yields were achieved by elongating the reaction time. Although the yields were only moderate, the reaction conditions were also applicable to N,N-dialkylanilines.
- Ide, Takafumi,Shimizu, Kazunori,Egami, Hiromichi,Hamashima, Yoshitaka
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supporting information
p. 3258 - 3261
(2018/07/25)
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- Cobalt(II)/ N -Hydroxyphthalimide-Catalyzed Cross-Dehydrogenative Coupling Reaction at Room Temperature under Aerobic Condition
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This work reports a cobalt(II)/N-hydroxyphthalimide (NHPI)-catalyzed cross-dehydrogenative oxidative coupling of N-aryl tetrahydroisoquinolines with various pro-nucleophiles, such as indoles, nitroalkanes, and trialkylphosphites, active methylene compound
- Patil, Mahendra R.,Dedhia, Noopur P.,Kapdi, Anant R.,Kumar, A.Vijay
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p. 4477 - 4490
(2018/04/26)
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- Luminescent Tungsten(VI) Complexes: Photophysics and Applicability to Organic Light-Emitting Diodes and Photocatalysis
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The synthesis, excited-state dynamics, and applications of two series of air-stable luminescent tungsten(VI) complexes are described. These tungsten(VI) complexes show phosphorescence in the solid state and in solutions with emission quantum yields up to 22 % in thin film (5 % in mCP) at room temperature. Complex 2 c, containing a 5,7-diphenyl-8-hydroxyquinolinate ligand, displays prompt fluorescence (blue–green) and phosphorescence (red) of comparable intensity, which could be used for ratiometric luminescent sensing. Solution-processed organic light-emitting diodes (OLEDs) based on 1 d showed a stable yellow emission with an external quantum efficiency (EQE) and luminance up to 4.79 % and 1400 cd m?2respectively. These tungsten(VI) complexes were also applied in light-induced aerobic oxidation reactions.
- Yeung, Kwan-Ting,To, Wai-Pong,Sun, Chenyue,Cheng, Gang,Ma, Chensheng,Tong, Glenna So Ming,Yang, Chen,Che, Chi-Ming
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supporting information
p. 133 - 137
(2016/12/30)
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- Luminescent Cyclometalated Gold(III) Alkyl Complexes: Photophysical and Photochemical Properties
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A series of luminescent cyclometalated gold(III) complexes having alkyls as auxiliary ligands has been prepared. The alkyl ligand was found to effectively increase the emission quantum yields and lifetimes of luminescent cyclometalated gold(III) complexes
- To, Wai-Pong,Tong, Glenna So Ming,Cheung, Chi-Wah,Yang, Chen,Zhou, Dongling,Che, Chi-Ming
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supporting information
p. 5046 - 5059
(2017/05/08)
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- Synthesis of α-aminonitriles via a FeSO4-mediated oxidative cyanation of tertiary amines with benzoyl cyanide and molecular oxygen or TBHP
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An iron-mediated oxidative cyanation of tertiary amines with benzoyl cyanide and molecular oxygen or TBHP has been achieved. This reaction furnished α-cyanated tertiary amines under mild reaction conditions in good to excellent yields (up to 94%) with gre
- Zhang, Lianpeng,Gu, Xin,Lu, Ping,Wang, Yanguang
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p. 2359 - 2363
(2016/04/19)
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- Approach to Isoindolinones, Isoquinolinones, and THIQs via Lewis Acid-Catalyzed Domino Strecker-Lactamization/Alkylations
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A one-pot, three-component synthesis of widely substituted isoindolinones and isoquinolinones, featuring a Lewis acid-catalyzed efficient Strecker reaction and lactamization sequence, affording products in good to high yields is reported. The method has also been extended to the synthesis of tetrahydroisoquinolines (THIQs) in high yields. (Chemical Equation Presented).
- Dhanasekaran, Sivasankaran,Suneja, Arun,Bisai, Vishnumaya,Singh, Vinod K.
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supporting information
p. 634 - 637
(2016/03/01)
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- Highly efficient and recyclable magnetic nanoparticles-supported gold(III)-bipy catalyst for oxidative α-cyanation of tertiary amines
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Oxidative α-cyanation of tertiary amines with trimethylsilyl cyanide was achieved by using a magnetic nanoparticles-supported gold(III)-bipy complex as catalyst to afford the corresponding α-aminonitriles in good to excellent yields in the presence of ter
- Yang, Weisen,Wei, Li,Yi, Feiyan,Cai, Mingzhong
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p. 4059 - 4067
(2016/07/06)
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- Tetrahydroisoquinoline compounds as preparing animal miticiding the application of the medicament
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The invention discloses application of a tetrahydroisoquinoline compound for preparing a drug killing animal mites. The compound has the molecular structure feature shown in the specification, wherein R is ortho-, meta- or para-alkyl, alkoxy, halogen, hydroxyl, nitro, trifluoromethyl, cyano group and the like. The compound has good activity in killing multiple animal mites like psoroptes communis cuniculi, which is superior to that of the clinical mite killing drug ivermectin, and has chemical stability and good compatibility with physiological environment.
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-
Paragraph 0032; 0055
(2016/10/07)
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- Photoredox catalysis under shear using thin film vortex microfluidics
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A microfluidic vortex fluidic device (VFD) operating in either confined or continuous mode is effective in high yielding photoredox reactions involving Rose Bengal, with short reaction times. This processing can be translated to multi-components reactions
- Gandy, Michael N.,Raston, Colin L.,Stubbs, Keith A.
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supporting information
p. 11041 - 11044
(2015/07/02)
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- α-Cyanation of Aromatic Tertiary Amines using Ferricyanide as a Non-Toxic Cyanide Source
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The reaction of aromatic tertiary amines with potassium ferricyanide directly provides the useful α-amino nitriles. The inexpensive iron complex functions both as an oxidant and as a cyanide source. The presence of molecular oxygen speeds up the reaction which can be performed in aqueous tert-butanol or even in ethanol-based mixtures like Tequila. While amine cyanations usually employ highly toxic cyanide sources, potassium ferricyanide is even less toxic than table salt. No expensive metal complexes are required as catalysts and the co-product of the cyanation, Prussian blue, has no known toxicity and is rather used as an antidote.
- Nauth, Alexander M.,Otto, Nicola,Opatz, Till
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supporting information
p. 3424 - 3428
(2016/01/25)
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- Potassium thiocyanate as source of cyanide for the oxidative α-cyanation of tertiary amines
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Oxidation at the sulfur of the safe-to-handle potassium thiocyanate releases cyanide units that are trapped in the presence of co-oxidized tertiary amines to form α-amino nitriles. These cyanations work in aqueous solutions and do not require a catalyst,
- Wagner, Alexander,Ofial, Armin R.
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p. 2848 - 2854
(2015/03/18)
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- Magnetically recyclable iron oxide nanoparticles for the α-cyanation of amines under acid-free conditions and the formal synthesis of praziquantel
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A sustainable protocol for the α-cyanation of amines has been developed using cheap and affordable iron oxide nanoparticles under acid free conditions with an easy-to-handle, user-friendly cyanide source, ethyl cyanoformate. The magnetic property of the i
- Patil, Mahendra,Kapdi, Anant R.,Kumar, A. Vijay
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p. 54505 - 54509
(2015/06/30)
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- A unique combined source of cN from 1,2-dichloroethane and TMSN3 in the copper-catalyzed cyanation of a C(sp3)-H bond adjacent to a nitrogen atom
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A novel combined metal-free CN source from trimethylsilyl azide and 1,2-dichloroethane has been developed and successfully applied to copper-catalyzed oxidative cyanation of α-C-H tertiary amines for the synthesis of C1-cyanation tetrahydroisoquinoline derivatives with good to excellent yields for the first time.
- Zhang, Gen,Ma, Yunxia,Cheng, Guangbin,Liu, Dabin,Wang, Rui
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supporting information
p. 656 - 659
(2014/03/21)
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- A class of promising acaricidal tetrahydroisoquinoline derivatives: Synthesis, biological evaluation and structure-activity relationships
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As part of our continuing research on isoquinoline acaricidal drugs, this paper reports the preparation of a series of the 2-aryl-1-cyano-1,2,3,4- tetrahydroisoquinolines with various substituents on the N-phenyl ring, their in vitro acaricidal activities against Psoroptes cuniculi, a mange mite, and discusses their SAR as well. The structures of all compounds, including 12 new ones, were elucidated by analysis of UV, IR, NMR, ESI-MS, HR-MS spectra and X-ray diffraction experiments. All target compounds showed varying degrees of activity at 0.4 mg/mL. Compound 1 showed the strongest activity, with a 50% lethal concentration value (LC50) of 0.2421 μg/mL and 50% lethal time value (LT50) of 7.79 h, comparable to the standard drug ivermectin (LC50 = 0.2474 μg/mL; LT50 = 20.9 h). The SAR showed that the substitution pattern on the N-aromatic ring exerted a significant effect on the activity. The substituents 2′-F, 3′-F, 2′-Cl, 2′-Br and 2′-CF3 remarkably enhanced the activity. Generally, for the isomers with the same substituents at different positions, the order of the activity was ortho > meta > para. It was concluded that the target compounds represent a class of novel promising candidates or lead compounds for the development of new tetrahydroisoquinoline acaricidal agents.
- Yang, Rui,Ruan, Qiao,Zhang, Bing-Yu,Zheng, Zuo-Lue,Miao, Fang,Zhou, Le,Geng, Hui-Ling
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p. 8051 - 8066
(2014/07/08)
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- Luminescent palladium(II) complexes with π-extended cyclometalated [R-C^N^N-R′] and pentafluorophenylacetylide ligands: Spectroscopic, photophysical, and photochemical properties
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A series of cyclometalated PdII complexes that contain π-extended R-C^N^N-R′ (R-C^N^N-R′=3-(6′-aryl-2′- pyridinyl)isoquinoline) and chloride/pentafluorophenylacetylide ligands have been synthesized and their photophysical and photochemical prop
- Chow, Pui-Keong,To, Wai-Pong,Low, Kam-Hung,Che, Chi-Ming
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p. 534 - 545
(2014/02/14)
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- Continuous flow organocatalytic C-H functionalization and cross-dehydrogenative coupling reactions: Visible light organophotocatalysis for multicomponent reactions and C-C, C-P bond formations
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A continuous flow procedure for the efficient metal-free, visible light photoredox-catalyzed α-functionalization of tertiary amines has been developed. Rose Bengal has been identified as an effective organic photocatalyst for continuous flow C-C and C-P b
- Rueping, Magnus,Vila, Carlos,Bootwicha, Teerawut
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p. 1676 - 1680
(2013/07/26)
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- A versatile C-H functionalization of tetrahydroisoquinolines catalyzed by iodine at aerobic conditions
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A versatile aerobic catalytic system (I2 and O2/TBHP) for C-H functionalization is reported. This CDC (cross-dehydrogentive coupling) reaction is compatible with a large number of nucleophiles and is performed under ambient reaction
- Dhineshkumar, Jayaraman,Lamani, Manjunath,Alagiri, Kaliyamoorthy,Prabhu, Kandikere Ramaiah
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supporting information
p. 1092 - 1095
(2013/03/29)
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- A robust palladium(II)-Porphyrin complex as catalyst for visible light induced oxidative C-H functionalization
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A series of palladium(II)-porphyrin complexes that display dual emissions with lifetimes up to 437μs have been synthesized. Among the four complexes, PdF20TPP is an efficient and robust catalyst for photoinduced oxidative C-H functionalization by using oxygen as terminal oxidant. α-Functionalized tertiary amines were obtained in good to excellent yields by light irradiation (λ>400nm) of a mixture of PdF20TPP, tertiary amine, and nucleophile (cyanide, nitromethane, dimethyl malonate, diethyl phosphite, and acetone) under aerobic conditions. Four examples of intramolecular cyclized amine compounds could be similarly prepared. Comparison of the UV-visible absorption spectra before and after the photochemical reaction revealed that PdF20TPP was highly robust (>95 % recovery). The practical application of PdF20TPP has been revealed by the photochemical reactions performed by using a low catalyst loading (0.01mol %) and on a 10mmol scale. The PdF20TPP catalyst could sensitize photoinduced oxidation of sulfides to sulfoxides in excellent yields. Mechanistic studies revealed that the photocatalysis proceeded by singlet-oxygen oxidation. Long-lived excited states! A series of palladium(II)-porphyrin complexes have been synthesized and found to display long-lived excited states with lifetimes up to 437μs (see scheme). Among these complexes, PdF 20TPP is an efficient and robust catalyst for a broad array of photoinduced oxidative C-H functionalization reactions. PtF20TPP= platinum(II) meso-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin.
- To, Wai-Pong,Liu, Yungen,Lau, Tai-Chu,Che, Chi-Ming
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supporting information
p. 5654 - 5664
(2013/06/04)
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- Light-mediated heterogeneous cross dehydrogenative coupling reactions: Metal oxides as efficient, recyclable, photoredox catalysts in C-C bond-forming reactions
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Let there be light: A heterogeneous photocatalytic system based on easily recyclable TiO2 or ZnO allows cross dehydrogenative coupling reactions of tertiary amines. The newly developed protocols have successfully been applied to various C-C and
- Rueping, Magnus,Zoller, Jochen,Fabry, David C.,Poscharny, Konstantin,Koenigs, Rene M.,Weirich, Thomas E.,Mayer, Joachim
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supporting information; experimental part
p. 3478 - 3481
(2012/04/23)
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- C-H functionalization of tertiary amines by cross dehydrogenative coupling reactions: Solvent-free synthesis of α-aminonitriles and β-nitroamines under aerobic condition
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A solvent-free synthesis of α-aminonitriles and β-nitroamines by oxidative cross-dehydrogenative coupling under aerobic condition is reported. A catalytic amount of molybdenum(vi) acetylacetonoate was found to catalyze cyanation of tertiary amines to form α-aminonitriles, whereas vanadium pentoxide was found to promote aza-Henry reaction to furnish β-nitroamines. Both of these environmentally benign reactions are performed in the absence of solvents using molecular oxygen as an oxidant.
- Alagiri, Kaliyamoorthy,Prabhu, Kandikere Ramaiah
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p. 835 - 842
(2012/02/05)
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- Luminescent organogold(III) complexes with long-lived triplet excited states for light-induced oxidative C-H bond functionalization and hydrogen production
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All that glitters is gold: Highly phosphorescent gold(III) complexes (see picture) with extended π-conjugated cyclometalating ligands exhibit rich photophysical and photochemical properties. They act as efficient photocatalysts/photosensitizers for oxidative functionalizations of secondary and tertiary benzylic amines and homogeneous hydrogen production from a water/acetonitrile mixture. Copyright
- To, Wai-Pong,Tong, Glenna So-Ming,Lu, Wei,Ma, Chensheng,Liu, Jia,Chow, Andy Lok-Fung,Che, Chi-Ming
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supporting information; experimental part
p. 2654 - 2657
(2012/04/17)
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- Visible-light photoredox catalyzed oxidative Strecker reaction
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An aerobic photocatalytic oxidative cyanation of tertiary amines providing valuable α-aminonitriles in good to excellent yields was developed. Mild reaction conditions and low catalyst loading are attractive features of the protocol. The Royal Society of
- Rueping, Magnus,Zhu, Shaoqun,Koenigs, Rene M.
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supporting information; experimental part
p. 12709 - 12711
(2012/01/05)
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- Eosin y catalyzed visible light oxidative C-C and C-P bond formation
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Eosin Y catalyzes efficiently the visible light mediated coupling of sp3 C-H bonds adjacent to the nitrogen atom in tetrahydroisoquinoline derivatives in the absence of an external oxidant. Nitroalkanes, dialkyl malonates, malononitrile, and di
- Hari, Durga Prasad,Koenig, Burkhard
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supporting information; experimental part
p. 3852 - 3855
(2011/09/19)
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- Graphene oxide and rose bengal: Oxidative C-H functionalisation of tertiary amines using visible light
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Visible light induced oxidative C-H functionalisation of tertiary amines catalysed by the combination of graphene oxide and Rose Bengal was developed. This reaction avoids the use of stoichiometric amounts of peroxy compounds as terminal oxidants. This re
- Pan, Yuanhang,Wang, Shuai,Kee, Choon Wee,Dubuisson, Emilie,Yang, Yuanyong,Loh, Kian Ping,Tan, Choon-Hong
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supporting information; experimental part
p. 3341 - 3344
(2012/01/06)
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- Iron catalyzed oxidative cyanation of tertiary amines
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Iron(ii) and iron(iii) salts catalyze the oxidative α-cyanation of tertiary amines by trimethylsilyl cyanide in the presence of tert-butylhydroperoxide under acid-free conditions at room temperature.
- Han, Wei,Ofial, Armin R.
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supporting information; scheme or table
p. 5024 - 5026
(2010/01/06)
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