- Efficient nitriding reagent and application thereof
-
The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
- -
-
Paragraph 0149-0151
(2021/03/31)
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- Ru-Catalyzed C(sp2)?H Bond Arylation of Benzamides Bearing a Novel 4-Aminoantipyrine as a Directing Group
-
A novel design-based removable N,O-bidentate directing group based on cheap and commercially available 4-aminoantipyrine (AAP) is reported. Aromatic AP amides bearing 4-aminoantipyrine underwent efficient Ru-catalyzed C(sp2)?H arylation using [RuCl2(PPh3)3] as a catalyst and aryl bromides as electrophiles. The novel bidentate directing group enabled the C?H functionalization reaction with good scope, good functional group tolerance and in decent yields.
- Al Mamari, Hamad H.,Al Kiumi, Diana,Al Rashdi, Tamadher,Al Quraini, Huda,Al Rashdi, Malak,Al Sheraiqi, Sumayya,Al Harmali, Sara,Al Lamki, Mohammed,Al Sheidi, Ahmed,Al Zadjali, Asma
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supporting information
p. 3598 - 3603
(2021/07/22)
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- Novel hybrid conjugates with dual estrogen receptor α degradation and histone deacetylase inhibitory activities for breast cancer therapy
-
Hormone therapy targeting estrogen receptors is widely used clinically for the treatment of breast cancer, such as tamoxifen, but most of them are partial agonists, which can cause serious side effects after long-term use. The use of selective estrogen receptor down-regulators (SERDs) may be an effective alternative to breast cancer therapy by directly degrading ERα protein to shut down ERα signaling. However, the solely clinically used SERD fulvestrant, is low orally bioavailable and requires intravenous injection, which severely limits its clinical application. On the other hand, double- or multi-target conjugates, which are able to synergize antitumor activity by different pathways, thus may enhance therapeutic effect in comparison with single targeted therapy. In this study, we designed and synthesized a series of novel dual-functional conjugates targeting both ERα degradation and histone deacetylase inhibiton by combining a privileged SERD skeleton 7-oxabicyclo[2.2.1]heptane sulfonamide (OBHSA) with a histone deacetylase inhibitor side chain. We found that substituents on both the sulfonamide nitrogen and phenyl group of OBHSA unit had significant effect on biological activities. Among them, conjugate 16i with N-methyl and naphthyl groups exhibited potent antiproliferative activity against MCF-7 cells, and excellent ERα degradation activity and HDACs inhibitory ability. A further molecular docking study indicated the interaction patterns of these conjugates with ERα, which may provide guidance to design novel SERDs or PROTAC-like SERDs for breast cancer therapy.
- Zhao, Chenxi,Tang, Chu,Li, Changhao,Ning, Wentao,Hu, Zhiye,Xin, Lilan,Zhou, Hai-Bing,Huang, Jian
-
-
- Nickel(II)- And Silver(I)-Catalyzed C-H Bond Halogenation of Anilides and Carbamates
-
ortho -C-H bond halogenation of anilides and N -aryl carbamates using easily available N -halosuccinimides (NXS) as the active halogenation reagent in the presence of nickel or silver catalyst has been developed. This method provides a new approach to 2-haloanilides and carbamates, which may serve as starting materials for the synthesis of pharmaceutically and biologically active compounds.
- Kianmehr, Ebrahim,Afaridoun, Hadi
-
supporting information
p. 1513 - 1523
(2020/12/14)
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- Acetonitrile and benzonitrile as versatile amino sources in copper-catalyzed mild electrochemical C-H amidation reactions
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A mild, efficient electrochemical approach to the site-selective direct C-H amidation of benzene and its derivatives with acetonitrile and benzonitrile has been developed. It has been shown that joint electrochemical oxidation of various arenes in the presence of a copper salt as a catalyst and nitriles leads to the formation of N-phenylacetamide from benzene and N-benzylacetamides from benzyl derivatives (up to 78% yield). A favorable feature of the process is mild conditions (room temperature, ambient pressure, no strong oxidants) that meet the criteria of green chemistry.
- Budnikova, Yulia,Kononov, Alexander,Rizvanov, Ildar,Strekalova, Sofia
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p. 37540 - 37543
(2021/12/07)
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- Catalyst-free generation of acyl radicals induced by visible light in water to construct C-N bonds
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We describe herein a catalyst-free and redox-neutral photochemical strategy for the direct generation of acyl radicals from α-diketones, and its selective conversion of nitrosoarenes to hydroxyamides or amides with AcOH or NaCl as an additive. The reaction was carried out under mild conditions in water with purple LEDs as the light source. A broad scope of substrates was demonstrated. Mechanistic experiments indicate that α-diketones cleave to give acyl radicals, with hydroxyamides being further reduced to amides.
- Ran, Maogang,He, Jiaxin,Yan, Boyu,Liu, Wenbo,Li, Yi,Fu, Yunfen,Li, Chao-Jun,Yao, Qiuli
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supporting information
p. 1970 - 1975
(2021/03/16)
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- Pd-Catalyzed Carbonylative Synthesis of 4H-Benzo[d][1,3]Oxazin-4-Ones Using Benzene-1,3,5-Triyl Triformate as the CO Source
-
A facile synthesis of 4H-benzo[d][1,3]oxazin-4-one derivatives by Pd-catalyzed carbonylative cross-coupling between N-(ortho-bromoaryl)amides and benzene-1,3,5-triyl triformate (TFBen) was developed. This procedure does not require the toxic and flammable gas CO as the carbonyl source and tolerates a wide scope of functional groups. Remarkably, 4H-benzo[d][1,3]oxazin-4-ones incorporated to natural products and drugs can be constructed by this method.
- Zheng, Yan,Dong, Mengke,Qu, Erdong,Bai, Jin,Wu, Xiao-Feng,Li, Wanfang
-
supporting information
p. 16219 - 16224
(2021/10/06)
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- Photocatalyst- And Transition-Metal-Free Visible-Light-Promoted Intramolecular C(sp2)-S Formation
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A photocatalyst- and transition-metal-free visible-light-induced cyclization of ortho-halothiobenzanilides has been developed. Upon irradiation with visible light, substrates undergo dehalogenative cyclization to 2-aryl benzothiazoles with high efficiency and selectivity. This photocyclization exhibits a high tolerance to various functional groups, is applicable for the synthesis of 2-alkyl benzothiazoles, and is easy to set up for gram-scale reaction.
- Wang, Hao,Wu, Qi,Zhang, Jian-Dong,Li, Hai-Yan,Li, Hong-Xi
-
supporting information
p. 2078 - 2083
(2021/04/05)
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- Direct para-Selective C-H Amination of Iodobenzenes: Highly Efficient Approach for the Synthesis of Diarylamines
-
Iodine(III)-mediated synthesis of 4-iodo-N-phenylaniline from iodobenzene has been achieved, and the reaction can proceed under mild conditions. A variety of functional groups were well tolerated, providing the corresponding products in moderate to good yields. The remaining iodine group provides an effective platform for converting the products into several valuable asymmetric diphenylamines. Most importantly, this reaction can be easily scaled up to the ten-gram scale, highlighting its synthetic utility. The mechanistic study revealed that the in situ generated aryl hypervalent iodine intermediate is the key factor to realize this para-selective C-H amination reaction.
- Chen, Yujie,Huang, Zhibin,Jiang, Yaqiqi,Shu, Sai,Yang, Shan,Shi, Da-Qing,Zhao, Yingsheng
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p. 8226 - 8235
(2021/06/28)
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- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
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The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
- Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
-
supporting information
p. 281 - 285
(2020/01/28)
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- Site-Specific Synthesis of Carbazole Derivatives through Aryl Homocoupling and Amination
-
We synthesized various carbazoles from anilines through a three-step process with good overall yields (up to 48percent). This process comprises N -acetylation, copper(0)-mediated Ullmann homocoupling, and acid-mediated intramolecular amination. It permits various functional groups on the substrate. Scale-up of the developed three-step synthetic route to carbazoles was also demonstrated.
- Baek, Junghyun,Ban, Jaeyoung,Lim, Minkyung,Rhee, Hakjune,Shabbir, Saira
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p. 917 - 927
(2020/03/13)
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- Rhodium-Catalyzed ortho-Bromination of O-Phenyl Carbamates Accelerated by a Secondary Amide-Pendant Cyclopentadienyl Ligand
-
It has been established that a newly developed cyclopentadienyl rhodium(III) [CpARhIII] complex, bearing an acidic secondary amide moiety on the Cp ring, is able to catalyze the ortho-bromination of O-phenyl carbamates with N-bromosuccinimide (NBS) at room temperature. The presence of the acidic secondary amide moiety on the CpA ligand accelerates the bromination by the hydrogen bond between the acidic NH group of the CpA ligand and the carbonyl group of NBS.
- Tanaka, Jin,Shibata, Yu,Joseph, Anton,Nogami, Juntaro,Terasawa, Jyunichi,Yoshimura, Ryo,Tanaka, Ken
-
supporting information
p. 5774 - 5779
(2020/05/08)
-
- Synthesis of diverse libraries of carboxamides via chemoselective N-acylation of amines by carboxylic acids employing Br?nsted acidic IL [BMIM(SO3H)][OTf]
-
Chemoselective N-acylation of amines with carboxylic acids as acyl electrophiles and Br?nsted acidic IL [BMIM(SO3H)][OTf] as promoter is reported under both thermal and microwave irradiation to produce libraries of carboxamides in good to excellent yields after a simple workup. The protocol is compatible with structurally diverse 1° and 2° amines and works in the presence of sensitive functional groups such as thiols and phenols. The potential for recycling and reuse of the IL is also demonstrated.
- Savanur, Hemantkumar M.,Malunavar, Shruti S.,Prabhala, Pavankumar,Sutar, Suraj M.,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
-
supporting information
(2019/09/30)
-
- KOtBu-Promoted Transition-Metal-Free Transamidation of Primary and Tertiary Amides with Amines
-
This work discloses transamidation of primary and tertiary amides with a range of aryl, heteroaryl, and aliphatic amines using potassium tert-butoxide. The reaction proceeds at room temperature under transition-metal-free conditions providing secondary amides in high yields. Moreover, reaction of cyclopropyl amine with tertiary amides proceeds with ring-opening to provide a rapid access to enamides.
- Ghosh, Tridev,Jana, Snehasish,Dash, Jyotirmayee
-
supporting information
p. 6690 - 6694
(2019/09/12)
-
- BENZOSULFONYL COMPOUNDS
-
Provided herein are compounds and pharmaceutical compositions comprising said compounds that are useful for treating cancers. Specific cancers include those that are mediated by YAP/TAZ or those that are modulated by the interaction between YAP/TAZ and TEAD.
- -
-
Paragraph 00439
(2019/03/12)
-
- Synthesis of Arylamides via Ritter-Type Cleavage of Solid-Supported Aryltriazenes
-
A novel route for the synthesis of N-arylamides via the cleavage of aryltriazenes with alkyl or aryl nitriles is presented. We developed a variation of the Ritter reaction that allows the use of acetonitrile as solvent and reagent in reactions with solid-supported precursors. The reaction was optimized for the generation of N-aryl acetamides using a diverse range of immobilized building blocks including o-, m-, and p-substituted aryltriazenes. The cleavage via the Ritter-type conversion was combined with an on-bead cross-coupling reaction of halogen-substituted aryltriazenes with pyrazoles. Additionally, the synthesis of on-bead generated arylboronic ester-substituted triazenes was shown. The developed procedure was further expanded to use other commercially available nitriles, such as acrylonitrile, benzonitrile, and chlorinated alkyl nitriles as suitable reagents for a Ritter-type cleavage of the prepared triazene linkers.
- Wippert, Nicolai A.,Jung, Nicole,Br?se, Stefan
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supporting information
p. 568 - 572
(2019/09/03)
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- Method for synthesizing N-phenylacetamide compounds
-
The present invention provides a method for synthesizing N-phenylacetamide compounds. The synthesis method takes an azide terminal olefin compound represented by a formula (I) as a raw material, sodium trifluoromethanesulfonate as an additive, potassium persulfate as an oxidant, and acetonitrile as a solvent, and a reaction is carried out at 80 DEG C for 5 hours, so that a corresponding target product is obtained. The synthesis method of the invention has the characteristics of small environmental hazard, mild reaction conditions, simple operation and the like.
- -
-
Paragraph 0027-0036
(2019/03/26)
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- Polystyrene-supported phosphine oxide-catalysed Beckmann rearrangement of ketoximes in 1,1,1,3,3,3-hexafluoro-2-propanol
-
A polystyrene-supported phosphine oxide-catalysed Beckmann rearrangement of ketoximes in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) has been developed. Good substrate compatibility, mild reaction conditions, good yields as well as the reusability of the catalyst/solvent made this procedure more environmentally benign.
- Wang, Yaoyao,Chen, Qun,He, Mingyang,Wang, Liang
-
p. 210 - 214
(2018/12/04)
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- 3-bromo-2-fluoronitrobenzene preparation method
-
The invention discloses a 3-bromo-2-fluoronitrobenzene preparation method. The method includes steps: (1) under the alkali action, subjecting bromoaniline and acetyl chloride to acetylation to obtainN-(2-bromophenyl)acetamide; (2) subjecting N-(2-bromophe
- -
-
Paragraph 0052-0063
(2019/10/23)
-
- Imidazolium chloride: An efficient catalyst for transamidation of primary amines
-
A highly efficient and convenient protocol of imidazolium chloride (30 mol %) catalyzed amidation of amines with moderate to excellent yields was reported. The protocol shows broad substrate scope for aromatic, aliphatic, and heterocyclic primary amines.
- Tian, Qingqiang,Gan, Zongjie,Wang, Xuetong,Li, Dan,Luo, Wen,Wang, Huajun,Dai, Zeshu,Yuan, Jianyong
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supporting information
(2018/09/10)
-
- Direct and Catalytic Amide Synthesis from Ketones via Transoximation and Beckmann Rearrangement under Mild Conditions
-
The Br?nsted acid-catalyzed synthesis of secondary amides from ketones under mild conditions is described via transoximation and Beckmann rearrangement using O-protected oximes as more stable equivalents of explosive O-protected hydroxylamines. This methodology could be applied to highly rearrangement-selective amide synthesis from α-branched alkyl aryl ketones and performed on a 1-g scale. The presence of water is essential for this reaction, and its role was clarified by isotope-labeling experiments.
- Hyodo, Kengo,Hasegawa, Genna,Oishi, Naoki,Kuroda, Kazuma,Uchida, Kingo
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p. 13080 - 13087
(2018/11/02)
-
- Synthesis and optical properties of 2-functionally substituted 4,5-dihydrothieno[3,2-c]quinolines
-
N-Protected 4-(anilinomethyl)thiophene-2-carbaldehydes were prepared by the reaction of easily available 4-chloromethylthiophene-2-carbaldehyde with N-(2-halogenophenyl) substituted acetamides, 4-methylbenzenesulfonamides and carbamates in the presence of K2CO3 or Cs2CO3. The compounds obtained were converted to 4,5-dihydrothieno [3,2-c]quinoline-2-carbaldehydes by palladium catalyzed intramolecular cyclization in homogenous or heterogenous (Pd/C) conditions with good yields and subsequently used for preparing of 2-functionally substituted thieno [3,2-c]quinoline derivatives (nitriles, carboxamides, carboxylic acids, esters). The optical properties of 2-functionally substituted thieno[3,2-c]quinolines and 4H-thieno[3,2-c]chromenes have been studied. Moderate to high fluorescence quantum yields are observed for these compounds ranging from 0.15 to 0.87. Structure - optical properties relationships have been established for the compounds synthesized, and their prospective application as invisible ink dyes was practically demonstrated.
- Bogza, Yulia P.,Rastrepin, Alexey A.,Nider, Victoria V.,Zheleznova, Tatyana Yu,Stasyuk, Anton J.,Kurowska, Aleksandra,Laba, Katarzyna,Ulyankin, Evgeny B.,Domagala, Wojciech,Fisyuk, Alexander S.
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p. 419 - 428
(2018/07/13)
-
- Cobalt(II)-catalyzed regioselective C-H halogenation of anilides
-
A cobalt-catalyzed regioselective C-H halogenation methodology is reported herein. The highlight of this work is the highly selective C-H functionalization of anilides, which results in high-yielding, versatile, and practical halogenated products. Thereby, brominations, chlorinations and iodinations of many electron-rich and electron-deficient anilides were achieved in a highly selective fashion. Mechanistic studies with respect to the pathway of the reaction are also described.
- Li, Ze-lin,Sun, Kang-kang,Cai, Chun
-
supporting information
p. 5433 - 5440
(2018/08/12)
-
- A Four-Step Synthesis of (±)-γ-Lycorane via Pd0-Catalyzed Double C(sp2)-H/C(sp3)-H Arylation
-
An expedient synthesis of lycorine alkaloids is reported using a palladium(0)-catalyzed double C-X/C-H arylation as the key step. The selectivity of this reaction was controlled through the judicious choice of the two halogen atoms, and its generality was
- Rocaboy, Ronan,Dailler, David,Baudoin, Olivier
-
supporting information
p. 772 - 775
(2018/02/09)
-
- Regioselective Halogenation of Arenes and Heterocycles in Hexafluoroisopropanol
-
Regioselective halogenation of arenes and heterocycles with N-halosuccinimides in fluorinated alcohols is disclosed. Under mild condition reactions, a wide diversity of halogenated arenes are obtained in good yields with high regioselectivity. Additionally, the versatility of the method is demonstrated by the development of one-pot sequential halogenation and halogenation-Suzuki cross-coupling reactions.
- Tang, Ren-Jin,Milcent, Thierry,Crousse, Benoit
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p. 930 - 938
(2018/01/28)
-
- Monoprotected l-Amino Acid (l-MPAA), Accelerated Bromination, Chlorination, and Iodination of C(sp2)?H Bonds by Iridium(III) Catalysis
-
Halogenated arenes are important structural motifs commonly found in biologically active molecules and used for a variety of transformations in organic synthesis. Herein, we report the mono-protected l-amino acid (l-MPAA) accelerated iridium(III)-catalyzed halogenation of (hetero)anilides at room temperature. This reaction constitutes the first example of an iridium(III)/l-MPAA-catalyzed general halogenation of (hetero)arenes through C(sp2)?H activation. Furthermore, we demonstrate the potential utility of our method through its use in the synthesis of a quinolone derivative.
- Kathiravan, Subban,Nicholls, Ian A.
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p. 7031 - 7036
(2017/05/29)
-
- Palladium-Catalyzed, ortho-Selective C-H Halogenation of Benzyl Nitriles, Aryl Weinreb Amides, and Anilides
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A palladium-catalyzed, ortho-selective C-H halogenation methodology is reported herein. The highlight of the work is the highly selective C(sp2)-H functionalization of benzyl nitriles in the presence of activated C(sp3)-H bond, which results in good yields of the halogenated products with excellent regioselectivity. Along with benzyl nitriles, aryl Weinreb amides and anilides have been evaluated for the transformation using aprotic conditions. Mechanistic studies yield interesting aspects with respect to the pathway of the reaction and the directing group abilities.
- Das, Riki,Kapur, Manmohan
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p. 1114 - 1126
(2018/06/18)
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- Palladium on Layered Double Hydroxide: A Heterogeneous System for the Enol Phosphate Carbon-Oxygen Bond Activation in Aqueous Media
-
In this work, a new catalytic approach for the C-O activation of enol phosphates based on a palladium supported on layered double hydroxide was developed. In this case, two different ketene aminal phosphates were used as models to study the synthesis of α
- Senra, Jaqueline D.,Silva, Aires C.,Santos, Raquel V.,Malta, Luiz Fernando B.,Simas, Alessandro B. C.
-
-
- Synthesis of 2-methylbenzoxazoles directly from: N -phenylacetamides catalyzed by palladium acetate
-
A method to synthesize 2-methylbenzoxazoles directly from N-phenylacetamides catalyzed by Pd(OAc)2 in the presence of K2S2O8 and TfOH has been developed. The desired products were obtained in moderate to excellent yields. This approach provides a facile procedure to prepare benzoxazoles with available substrates. It is found that TfOH is the key factor for this cyclization reaction. A plausible mechanism of the reaction is proposed according to the control reactions and the literature.
- Wang, Biying,Jiang, Chengfei,Qian, Jiasheng,Zhang, Shuwei,Jia, Xiaodong,Yuan, Yu
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p. 101 - 107
(2017/12/27)
-
- Directed C?H Activation and Tandem Cross-Coupling Reactions Using Palladium Nanocatalysts with Controlled Oxidation
-
Controlled oxidation of palladium nanoparticles provided high-valent PdIV oxo-clusters which efficiently promote directed C?H halogenation reactions. In addition, palladium nanoparticles can undergo changes in oxidation states to provide both high-valent PdIV and low-valent Pd0 species within one system, and thus a tandem reaction of C?H halogenation and cross-coupling (C?N, C?C, and C?S bond formation) was successfully established.
- Kim, Kiseong,Jung, Younjae,Lee, Suyeon,Kim, Mijong,Shin, Dongwoo,Byun, Hyeeun,Cho, Sung June,Song, Hyunjoon,Kim, Hyunwoo
-
supporting information
p. 6952 - 6956
(2017/06/06)
-
- Electrosynthesis using a recyclable mediator-electrolyte system based on ionically tagged phenyl iodide and 1,1,1,3,3,3-hexafluoroisopropanol
-
A new type of redox mediator for electrosynthesis based on the iodine(I)/iodine(III) redox couple is reported. It is demonstrated that the use of 1,1,1,3,3,3-hexafluoroisopropanol as solvent plays a crucial role for both the selective anodic generation of the active iodine(III) species and the subsequent chemical transformation. Furthermore, the supporting electrolyte is merged with the mediator by tethering the redox-active iodophenyl moiety to an alkylammonium group, allowing for straightforward recovery and reuse of both components.
- Broese, Timo,Francke, Robert
-
supporting information
p. 5896 - 5899
(2016/11/29)
-
- Mild and efficient palladium-catalyzed direct trifluoroethylation of aromatic systems by C-H activation
-
The introduction of trifluoroalkyl groups into aromatic molecules is an important transformation in the field of organic and medicinal chemistry. However, the direct installation of fluoroalkyl groups onto aromatic molecules still represents a challenging and highly demanding synthetic task. Herein, a simple trifluoroethylation process that relies on the palladium-catalyzed C-H activation of aromatic compounds is described. With the utilization of a highly active trifluoroethyl(mesityl)iodonium salt, the developed catalytic method enables the first highly efficient and selective trifluoroethylation of aromatic compounds. The robust catalytic procedure provides the desired products in up to 95 % yield at 25 °C in 1.5 to 3 hours and tolerates a broad range of functional groups. The utilization of hypervalent reagents opens new synthetic possibilities for direct alkylations and fluoroalkylations in the field of transition-metal-catalyzed C-H activation.
- T?th, Balázs L.,Kovács, Szabolcs,Sályi, Gerg?,Novák, Zoltán
-
supporting information
p. 1988 - 1992
(2016/02/18)
-
- Nickel(0)-Catalyzed N-Allylation of Amides and p-Toluenesulfonamide with Allylic Alcohols under Neat and Neutral Conditions
-
Nickel(0)-catalyzed direct N-allylation of amides and p-toluenesulfonamide with allylic alcohols took place in the presence of Ni0–diphosphine complexes. The corresponding N-allylated (and/or N,N-diallylated) products were obtained in moderate to high yields under neutral conditions.
- Azizi, Mohamed Salah,Edder, Youssef,Karim, Abdallah,Sauthier, Mathieu
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p. 3796 - 3803
(2016/08/16)
-
- Selective N-acetylation of aromatic amines using acetonitrile as acylating agent
-
A method for N-acetylation of amines has been developed using acetonitrile as an acylating agent and in situ generated trimethylsilyl iodide as the catalyst under microwave heating condition. The reaction is selective toward aromatic amines while aliphatic amines remain intact. The process eliminates the requirement of toxic acylating reagents like acetic anhydride and acetyl chloride.
- Saikia, Ujwal Pratim,Hussain, Farhaz L.,Suri, Mrinaly,Pahari, Pallab
-
supporting information
p. 1158 - 1160
(2016/03/09)
-
- Synthesis of secondary amides from N-Substituted amidines by tandem oxidative rearrangement and isocyanate elimination
-
In this work an efficient tandem process transforming N-substituted amidines into secondary amides has been described. The process involves N-acylurea formation by reaction of the substrate with bis(acyloxy)(phenyl)-λ3-iodane followed by isocyanate elimination. The periodinane reagents are obtained from the commercially available phenyl-iodine(III) diacetate [PhI(OAc)2, (PIDA)] by ligand exchange with carboxylic acids. The N-substituted amidine substrates are easily synthesized from readily available nitriles. The method is applicable for secondary amide synthesis, based on both aliphatic and (hetero)aromatic amines, including challenging amides consisting of sterically hindered acids and amines. Moreover, the protocol allows one to combine steric bulk with electron deficiency in the target amides (aniline based). Such compounds are difficult to synthesize efficiently based on classical condensation reactions involving carboxylic acids and amines. Overall, the synthetic protocol transforms a nitrile into a secondary amide in both aliphatic and (hetero)aromatic systems.
- Debnath, Pradip,Baeten, Mattijs,Lefvre, Nicolas,Van Daele, Stijn,Maes, Bert U. W.
-
supporting information
p. 197 - 209
(2015/03/03)
-
- SUBSTITUTED DIAMINOPYRIMIDYL COMPOUNDS, COMPOSITIONS THEREOF, AND METHODS OF TREATMENT THEREWITH
-
Provided herein are diaminopyrimidyl Compounds having the following structures: wherein X, L, R1, and R2 are as defined herein, compositions comprising an effective amount of a Diaminopyrimidyl Compound, and methods for treating or preventing PKC-theta-mediated disorders, or a condition treatable or preventable by inhibition of a kinase, for example, PKC-theta.
- -
-
Paragraph 0185
(2015/07/02)
-
- One-pot oximation-Beckmann rearrangement of ketones and aldehydes to amides of industrial interest: Acetanilide, caprolactam and acetaminophen
-
High yielding one-pot oximation-Beckmann rearrangement of ketones to amides in ktrifluoroacetic acid has been conducted on several ketones and aldehydes. The substrate reactivity showed to depend on both oximation and Beckmann rearrangement reaction rate. In this synthetic procedure, trifluoroacetic acid acts as solvent, acid catalyst and organocatalyst and can be easily recycled.
- Aricò, Fabio,Quartarone, Giuseppe,Rancan, Elia,Ronchin, Lucio,Tundo, Pietro,Vavasori, Andrea
-
-
- The beckmann rearrangement executed by visible-light-driven generation of vilsmeier-haack reagent
-
A new and efficient approach for the Beckmann rearrangement is reported. The protocol involves eosin? Y catalyzed, visible-light-mediated in situ formation of the Vilsmeier-Haack reagent from CBr4 and a catalytic amount of DMF for activation of ketoximes at room temperature. The method is operationally simple and avoids the need for any corrosive, water-sensitive reagents and elevated temperatures. Georg Thieme Verlag Stuttgart New York.
- Srivastava, Vishnu P.,Yadav, Arvind K.,Yadav, Lal Dhar S.
-
supporting information
p. 665 - 670
(2014/04/03)
-
- Palladium-catalyzed carbonylative synthesis of benzoxazinones from N -(o -bromoaryl)amides using paraformaldehyde as the carbonyl source
-
Carbonylation reactions have been widely used in organic synthesis. However, the manipulation of toxic and pressurized carbon monoxide limited their applications in organic laboratories. The search for alternative carbonyl sources as an important method for carbonylative organic synthesis is spreading. Herein, a series of substituted benzoxazinones were synthesized from N-(o-bromoaryl)amides by palladium-catalyzed carbonylation with paraformaldehyde as the carbonyl source, which is inexpensive, stable, and easy to use. Notably, this is the first example of using paraformaldehyde as the CO source in palladium-catalyzed carbonylative synthesis of heterocycles.
- Li, Wanfang,Wu, Xiao-Feng
-
p. 10410 - 10416
(2015/02/19)
-
- One-pot preparation of 2-(alkyl)arylbenzoselenazoles from the corresponding N-(acetyl)benzoyl-2-iodoanilines via a microwave-assisted methodology
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We report here the first example of a one-pot synthesis of 2-(alkyl)arylbenzoselenazoles from N-(acetyl)benzoyl-2-iodoanilines. The reaction was carried out in the presence of Woollins' reagent under microwave irradiation and resulted in moderate to good yields.
- Redon, Sébastien,Kabri, Youssef,Crozet, Maxime D.,Vanelle, Patrice
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supporting information
p. 5052 - 5054
(2015/01/09)
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- Practical and metal-free electrophilic aromatic halogenation by interhalogen compounds generated in situ from N-halosuccinimide and catalytic TMSCL
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Halomonochloride compounds (ClCl, BrCl, ICl) generated in situ from N-halosuccinimide and catalytic chlorotrimethylsilane (TMSCl, 0.1 equiv) can efficiently halogenate aromatic compounds to give halogenated products in good to excellent yields and selectivities. The reaction can be carried out at room temperature or at lower temperatures, requires only one hour, is practical to apply to a wide range of substrates, and provides a simple access to a variety of haloarene compounds. Georg Thieme Verlag Stuttgart New York.
- Maibunkaew, Tapanee,Thongsornkleeb, Charnsak,Tummatorn, Jumreang,Bunrit, Anon,Ruchirawat, Somsak
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supporting information
p. 1769 - 1775
(2014/08/05)
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- Synthesis of polycyclic aminocyclobutane systems by the rearrangement of N-(ortho-Vinylphenyl) 2-Azabicyclo[3.1.0]hexane derivatives
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The acid-catalysed thermal rearrangements of a family of N-aryl 2-azabicyclo[3.1.0]hexanes is described. These substrates, designed in such a way that the aromatic system is conjugated with an alkene group located at the ortho position relative to the nitrogen atom, have been prepared by using an intramolecular Kulinkovich-de Meijere reaction. The rearrangements can then be conducted either under standard thermal conditions or with microwave activation. Depending on the conditions applied and the substitution pattern, dihydroquinoline or polycyclic aminocyclobutane derivatives can be obtained. A mechanistic discussion is provided, with the proposition of the initial protonation of the aminocyclopropane moiety to give an iminium intermediate. By analogy with related intermolecular reactions, the involvement of electrocyclic reactions among the series of elementary steps that follow is put forward. Small rings: The acid-catalysed rearrangement of bicyclic N-aryl aminocyclopropanes with an alkene group located at the ortho position, either under standard thermal conditions or with microwave activation, is described (see scheme). The method provides access to dihydroquinoline and polycyclic aminocyclobutane derivatives. By analogy with related intermolecular reactions, the involvement of an electrocyclic reaction is proposed. Copyright
- Wasilewska, Agnieszka,Wozniak, Bartosz A.,Doridot, Gabriel,Piotrowska, Kamila,Witkowska, Natalia,Retailleau, Pascal,Six, Yvan
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supporting information
p. 11759 - 11767
(2013/09/12)
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- Oxidative para- Triflation of acetanilides
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Direct triflation of acetanilide derivatives with silver triflate has been accomplished under mild iodine(III)-mediated oxidative conditions. The reaction shows excellent regioselectivity for the para position and tolerates a range of ortho and meta substituents on the aromatic ring. This method is also compatible with the preparation of arylnonaflates in synthetically useful yields.
- Pialat, Amelie,Liegault, Benoit,Taillefer, Marc
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supporting information
p. 1764 - 1767
(2013/06/26)
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- Photoredox transformations with dimeric gold complexes
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Let the sunshine in! Unactivated alkyl and aryl bromides underwent a light-enabled reductive radical cyclization in the presence of a dimeric phosphine-gold complex as a photocatalyst (see scheme; X=C(CO 2Et)2, NR, O). Sunlight can be used as the energy source for this simple and efficient radical reaction, which does not require potentially hazardous and toxic chemical reagents, such as organostannanes and chemical initiators.
- Revol, Guillaume,McCallum, Terry,Morin, Mathieu,Gagosz, Fabien,Barriault, Louis
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supporting information
p. 13342 - 13345
(2014/01/06)
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- A novel green route for the synthesis of N-phenylacetamides, benzimidazoles and acridinediones using Candida parapsilosis ATCC 7330
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Biocatalytic preparation of various substituted N-phenylacetamides was carried out for the first time using whole cells of Candida parapsilosis ATCC 7330 under mild reaction conditions with excellent conversions (up to 93%) and good yields (up to 81%). Arylamine N-acetyltransferase (NAT) from whole cells of Candida parapsilosis ATCC 7330 is implicated in the N-acylation which is known to transfer the acetyl group from acetyl CoA (coenzyme A) to aromatic amines. Mechanistic investigation carried out using deuterated ethanol to find the source of acetyl CoA revealed that the reaction proceeds through the formation of acetaldehyde in situ, which is a potential source for the acetyl group of cytoplasmic acetyl CoA. Furthermore, experiments on regioselectivity, carried out with 2-phenylenediamine (2-PDA) resulted in a cyclised product 2-methyl benzimidazole (conversion 99%). The biocatalyst also mediates the cyclization of 3-(phenylamino)cyclohex-2-enones in the presence of the in situ generated acetaldehyde to form acridine-1,8-diones (conversion up to 70%), which is a green process reported here for the first time. The Royal Society of Chemistry 2013.
- Mahajabeen, Pula,Chadha, Anju
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p. 21972 - 21980
(2013/11/06)
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- Regioselective control of aromatic halogenation reactions in carbon nanotube nanoreactors
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The use of single-walled carbon nanotubes as effective nanoreactors for preparative chemical reactions has been demonstrated for the first time. Extreme spatial confinement of reactant molecules inside nanotubes has been shown to drastically affect both the regioselectivity and kinetics of aromatic halogenation reactions.
- Miners, Scott A.,Rance, Graham A.,Khlobystov, Andrei N.
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supporting information
p. 5586 - 5588
(2013/07/25)
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- A general palladium-catalyzed carbonylative synthesis of 2-alkylbenzoxazinones from 2-bromoanilines and acid anhydrides
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(C), its (O)K! An efficient palladium-catalyzed carbonylative synthesis of 2-alkylbenzoxazinones has been developed (see scheme). By starting from 2-bromoanilines and acid anhydrides, the corresponding products were isolated in good yields. Copyright
- Wu, Xiao-Feng,Neumann, Helfried,Beller, Matthias
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p. 12599 - 12602
(2012/11/07)
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- High-yielding, versatile, and practical [Rh(III)Cp*]-catalyzed ortho bromination and iodination of arenes
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We report a uniquely high-yielding, general, and practical ortho bromination and iodination reaction of different classes of aromatic compounds. This reaction occurs by Rh(III)-catalyzed C-H bond activation methodology and is therefore the first example of the application of this cationic catalyst for C-Br and C-I bond formation.
- Schroeder, Nils,Wencel-Delord, Joanna,Glorius, Frank
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supporting information; experimental part
p. 8298 - 8301
(2012/06/29)
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- Efficient amide formation from arylamines and esters promoted by AlCl 3/Et3N: An experimental and computational investigation
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Efficient and selective preparation of amides from arylamines and esters has been achieved with an AlCl3/Et3N pair under mild conditions. A large number of arylamines were successfully acylated to the corresponding amides in high yields and short reaction times. For instance, a 94% yield of p-bromoacetanilide was obtained from p-bromoaniline and ethyl acetate in 10 min at room temperature. In addition, a computational study on the N-acylation of amines was performed using density functional theory. It was found that the energy barrier for N-acylation of aniline is 10 kcal/mol higher than that of methylamine. In the presence of AlCl3, the activation energy for the N-acylation of aniline was reduced by 27.7 kcal/mol with the endothermic process becoming exothermic. Springer Science+Business Media B.V. 2012.
- Tong, Xinli,Ren, Zhangshun,Que, Xiaolong,Yang, Qiwu,Zhang, Wenqin
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p. 1961 - 1968
(2013/02/22)
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- Selectivity enhancement of aromatic halogenation reactions at the micellar interface: Effect of highly ionic media
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Halogenation (iodination and bromination) of various aromatic compounds has been studied in micellar media in order to observe the effect on regioselectivity and conversion of the reaction. The addition of surfactant causes a change in the chemical shifts of the aromatic proton resonance of phenol which proves the orientation of the aromatic compound on the micellar surface. However, increase in ionic strength of the reaction media affects the selectivity of reaction by disturbing this spatial orientation of the aromatic compound in the micelle. Selectivity towards particular isomers is dependent on the concentration of the surfactant. In bromination of chlorobenzene (deactivated aromatic compound) enhancement in selectivity and conversion towards the para isomer has been observed.
- Samant, Bhupesh S.,Bhagwat, Sunil S.
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scheme or table
p. 1039 - 1044
(2012/10/18)
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