3287-99-8Relevant articles and documents
Magnetocaloric effect and critical behavior in arylamine-based copper chloride layered organic-inorganic perovskite
Blake, Graeme R.,Septiany, Liany
, (2021/10/04)
Layered organic-inorganic hybrid perovskites have been the focus of much research regarding their optoelectronic and multiferroic properties. Here, we demonstrate the presence of a large magnetocaloric effect in the ferromagnetic layered perovskite phenylmethylammonium copper chloride ((PMA)2CuCl4) below the Curie temperature of ～9.5 K. We measure a magnetic entropy change ranging from 0.88 J/kg.K to 2.98 J/kg.K in applied fields of 10 kOe and 70 kOe, respectively. We also study the nature of the magnetic phase transition using critical isotherm analysis. The critical exponents are consistent with the 2D-XY spin model.
Tandem Fe/Zn or Fe/In Catalysis for the Selective Synthesis of Primary and Secondary Amines?via Selective Reduction of Primary Amides
Darcel, Christophe,Wu, Jiajun
, (2022/03/18)
Tandem iron/zinc or iron/indium-catalysed reductions of various primary amides to amines under hydrosilylation conditions are reported under visible light activation. By a simple modification of the nature of the co-catalyst (Zn(OTf)2 vs In(OTf)3), Fe(CO)4(IMes) can promote the highly chemoselective reduction of primary amides into primary amines (21 examples, up to 93 % isolated yields) and secondary amines (8 examples, up to 51 % isolated yields), respectively. Notably, both benzamide and alkanamide derivatives can be reduced.
Hydrosilylative reduction of primary amides to primary amines catalyzed by a terminal [Ni-OH] complex
Bera, Jitendra K.,Pandey, Pragati
supporting information, p. 9204 - 9207 (2021/09/20)
A terminal [Ni-OH] complex1, supported by triflamide-functionalized NHC ligands, catalyzes the hydrosilylative reduction of a range of primary amides into primary amines in good to excellent yields under base-free conditions with key functional group tolerance. Catalyst1is also effective for the reduction of a variety of tertiary and secondary amides. In contrast to literature reports, the reactivity of1towards amide reduction follows an inverse trend,i.e., 1° amide > 3° amide > 2° amide. The reaction does not follow a usual dehydration pathway.
Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
An, Duk Keun,Jaladi, Ashok Kumar,Kim, Hyun Tae,Yi, Jaeeun
, (2021/11/17)
Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
Green method for catalyzing reduction reaction of aliphatic nitro derivative
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Paragraph 0005-0006; 0049-0052, (2021/07/31)
The invention relates to a green method for catalyzing reduction reaction of aliphatic nitro derivatives. According to the method, non-transition metal compounds, namely triethyl boron and potassium tert-butoxide, are used as a catalytic system for the first time, an aliphatic nitro derivative and pinacolborane which is low in price and easy to obtain are catalyzed to be subjected to a reduction reaction under mild conditions, and an aliphatic amine hydrochloride product is synthesized after acidification with a hydrochloric acid aqueous solution. Compared with a traditional method, the method generally has the advantages that the catalyst is cheap and easy to obtain, operation is convenient, and reaction is safe. The selective reduction reaction of the aliphatic nitro derivative catalyzed by the non-transition metal catalyst and pinacol borane is realized for the first time, and the aliphatic amine hydrochloride product is synthesized through acidification treatment of the hydrochloric acid aqueous solution, so that a practical new reaction strategy is provided for laboratory preparation or industrial production.
Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
supporting information, p. 1618 - 1629 (2021/01/25)
Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
Silver-Catalyzed Hydroboration of C-X (X = C, O, N) Multiple Bonds
Pandey, Vipin K.,Tiwari, Chandra Shekhar,Rit, Arnab
supporting information, p. 1681 - 1686 (2021/03/03)
AgSbF6 was developed as an effective catalyst for the hydroboration of various unsaturated functionalities (nitriles, alkenes, and aldehydes). This atom-economic chemoselective protocol works effectively under low catalyst loading, base- A nd solvent-free moderate conditions. Importantly, this process shows excellent functional group tolerance and compatibility with structurally and electronically diverse substrates (>50 examples). Mechanistic investigations revealed that the reaction proceeds via a radical pathway. Further, the obtained N,N-diborylamines were showcased to be useful precursors for amide synthesis.
Deoxygenative hydroboration of primary and secondary amides: a catalyst-free and solvent-free approach
Bisai, Milan Kumar,Jain, Shailja,Kumar, Rohit,Sen, Sakya S.,Vanka, Kumar
supporting information, p. 10596 - 10599 (2021/10/19)
In contrast to the recent reports on catalytic hydroboration of amides to amines with pinacolborane (HBpin), a simple catalyst-free and solvent-free method for the hydroboration of a variety of amides has been realized. To get the mechanistic insights, DFT calculations have been performed.
Lithium compound catalyzed deoxygenative hydroboration of primary, secondary and tertiary amides
Bisai, Milan Kumar,Gour, Kritika,Das, Tamal,Vanka, Kumar,Sen, Sakya S.
supporting information, p. 2354 - 2358 (2021/03/03)
A selective and efficient route for the deoxygenative reduction of primary to tertiary amides to corresponding amines has been achieved with pinacolborane (HBpin) using simple and readily accessible 2,6-di-tert-butyl phenolate lithium·THF (1a) as a catalyst. Both experimental and DFT studies provide mechanistic insight. This journal is
Reduction of Amides to Amines with Pinacolborane Catalyzed by Heterogeneous Lanthanum Catalyst La(CH2C6H4NMe2- o)3@SBA-15
Guo, Chenjun,Zhang, Fangcao,Yu, Chong,Luo, Yunjie
supporting information, p. 13122 - 13135 (2021/08/31)
Hydroboration of amides is a useful synthetic strategy to access the corresponding amines. In this contribution, it was found that the supported lanthanum benzyl material La(CH2C6H4NMe2-o)3@SBA-15 was highly active for the hydroboration of primary, secondary, and tertiary amides to amines with pinacolborane. These reactions selectively produced target amines and showed good tolerance for functional groups such as -NO2, -halogen, and -CN, as well as heteroatoms such as S and O. This reduction procedure exhibited the recyclable and reusable property of heterogeneous catalysts and was applicable to gram-scale synthesis. The reaction mechanisms were proposed based on some control experiments and the previous literature. This is the first example of hydroborative reduction of amides to amines mediated by heterogeneous catalysts.
