14657-86-4Relevant academic research and scientific papers
Pd-Catalyzed Oxidative Aminocarbonylation of Arylboronic Acids with Unreactive Tertiary Amines via C-N Bond Activation
Kolekar, Yuvraj A.,Bhanage, Bhalchandra M.
, p. 14028 - 14035 (2021/05/29)
An efficient synthesis of tertiary amides from aryl boronic acids and inert tertiary amines through the oxidative carbonylation via C(sp3)-N bond activation is presented. This protocol significantly restricts the homocoupling biarylketone product. It involves the use of a homogeneous PdCl2/CuI catalyst and a heterogeneous Pd/C based catalyst, which promotes C(sp3)-N bond activation of tertiary amines with aryl boronic acids. This process represents a ligand-free, base-free, and recyclable catalyst along with an ideal oxidant like molecular oxygen.
One-Pot Synthesis of Tertiary Amides from Organic Trichlorides through Oxygen Atom Incorporation from Air by Convergent Paired Electrolysis
Luo, Zhongli,Imamura, Kenji,Shiota, Yoshihito,Yoshizawa, Kazunari,Hisaeda, Yoshio,Shimakoshi, Hisashi
, p. 5983 - 5990 (2021/05/04)
A convergent paired electrolysis catalyzed by a B12 complex for the one-pot synthesis of a tertiary amide from organic trichlorides (R-CCl3) has been developed. Various readily available organic trichlorides, such as benzotrichloride and its derivatives, chloroform, dichlorodiphenyltrichloroethane (DDT), trichloro-2,2,2-trifluoroethane (CFC-113a), and trichloroacetonitrile (CNCCl3), were converted to amides in the presence of tertiary amines through oxygen incorporation from air at room temperature. The amide formation mechanism in the paired electrolysis, which was mediated by a cobalt complex, was proposed.
Tandem Photoredox Catalysis: Enabling Carbonylative Amidation of Aryl and Alkylhalides
Connell, Timothy U.,Forni, José A.,Micic, Nenad,Polyzos, Anastasios,Weragoda, Geethika
supporting information, p. 18646 - 18654 (2020/08/21)
We report a new visible-light-mediated carbonylative amidation of aryl, heteroaryl, and alkyl halides. A tandem catalytic cycle of [Ir(ppy)2(dtb-bpy)]+ generates a potent iridium photoreductant through a second catalytic cycle in the presence of DIPEA, which productively engages aryl bromides, iodides, and even chlorides as well as primary, secondary, and tertiary alkyl iodides. The versatile in situ generated catalyst is compatible with aliphatic and aromatic amines, shows high functional-group tolerance, and enables the late-stage amidation of complex natural products.
Amine-Mediated Bond Cleavage in Oxidized Lignin Models
Li, Hongji,Liu, Meijiang,Liu, Huifang,Luo, Nengchao,Zhang, Chaofeng,Wang, Feng
, p. 4660 - 4665 (2020/07/04)
Introducing amines/ammonia into lignin cracking will allow novel bond cleavage pathways. Herein, a method of amines/ammonia-mediated bond cleavage in oxidized lignin β-O-4 models was studied using a copper catalyst at room temperature, demonstrating the effect of the amine source on the selectivity of products. For primary and secondary aliphatic amines, lignin ketone models underwent oxidative Cα?Cβ bond cleavage and Cα?N bond formation to generate aromatic amides. For ammonia, the competition between oxygen and ammonia determined the selectivity between Cα?N and Cβ?N bond formation, generating amides and α-keto amides, respectively. For tertiary amines, the lignin models underwent oxidative Cα?Cβ bond cleavage to benzoic acids. Control experiments indicated that amines act as nucleophiles attacking at the Cα or Cβ position of the oxidized β-O-4 linkage to be cleaved. This study represents a novel example that the breakage of oxidized lignin model can be regulated by amines with a copper catalyst.
Tris(o-phenylenedioxy)cyclotriphosphazene as a Promoter for the Formation of Amide Bonds between Aromatic Acids and Amines
Movahed, Farzaneh Soleymani,Sawant, Dinesh N.,Bagal, Dattatraya B.,Saito, Susumu
, p. 3253 - 3262 (2020/11/02)
The atom-efficient formation of amide bonds has emerged as a top-priority research field in organic synthesis, as amide bonds constitute the backbones of proteins and represent an important structural motif in drug molecules. Currently, the increasing demand for novel discoveries in this field has focused substantial attention on this challenging subject. Herein, the degradable 1,3,5-triazo-2,4,6-triphosphorine (TAP) motif is presented as a new condensation system for the dehydrative formation of amide bonds between diverse combinations of aromatic carboxylic acids and amines. The underlying reaction mechanism was investigated, and potential catalyst intermediates were characterized using 31 P NMR spectroscopy and ESI mass spectrometry.
Synthesis of a B12-BODIPY dyad for B12-inspired photochemical transformations of a trichloromethylated organic compound
Anai, Yuki,Shichijo, Keita,Fujitsuka, Mamoru,Hisaeda, Yoshio,Shimakoshi, Hisashi
, p. 11945 - 11948 (2020/10/15)
A B12complex-BODIPY dyad was synthesized by peripheral modification of cobalamin derivatives. The photophysical properties of the dyad were investigated by UV-vis, PL, and transient absorption spectroscopy. A visible light-driven dechlorination reaction of a trichlorinated organic compound, DDT, was reported. The dyad showed efficient catalysis for dechlorination under N2with turnover numbers of over 220 for the reaction. One-pot syntheses of an ester and amide from DDT and benzotrichloride were also achieved using the dyad under air.
Visible light-driven photocatalytic duet reaction catalyzed by the B12-rhodium-titanium oxide hybrid catalyst
Shichijo, Keita,Fujitsuka, Mamoru,Hisaeda, Yoshio,Shimakoshi, Hisashi
supporting information, (2019/12/24)
The hybrid catalyst composed of the B12 complex and rhodium ion (Rh3+) modified titanium oxide was synthesized for the visible light-driven B12 inspired catalytic reaction. The hybrid catalyst contains 4.93 × 10?6 molg?1 of the B12 complex and 5.43 × 10?5 molg?1 of the Rh(III) ion on the surface of titanium oxide. Visible light irradiation (λ ≧ 420 nm) of the hybrid catalyst in the presence of triethylamine (Et3N) as a sacrificial reagent showed absorption at 390 nm, typical for the Co(I) state of the B12 complex monitored by diffuse reflectance UV–vis analysis, which imply that electron transfer from the titanium oxide to Co(III) center of the B12 complex occurred by the visible light irradiation. Benzotrichloride was converted to N,N-diethylbenzamide by the visible light irradiation catalyzed by the hybrid catalyst in air at room temperature. Both the conduction band electron and valence band hole of the catalyst were utilized for the reaction to form the amide product. The reaction mechanism of the duet reaction was proposed.
A room temperature next amine control lignin model molecular breaking method
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Paragraph 0038; 0039; 0070; 0072, (2019/06/30)
The invention relates to a room temperature next amine control lignin model molecular breaking method. The method adopts the 1 - aryl - 2 - [...] as lignin β - O - 4 model molecule, in under the action of the copper salt and an amine, is oxidized and broken C - C/C - O key; wherein a primary and secondary aliphatic amine control into aromatic amide and a phenolic compound, inorganic ammonia control generating α - one amide and phenolic compound, tertiary amine control into aromatic acid and phenol compounds. The testing process are as follows: the 1 - aryl - 2 - [...], amine compound with a copper salt in dimethyl sulfoxide in mixed, put in the pressure container, the charge air or oxygen after the replacement is closed, at room temperature, stirring the reaction 8 - 12 is H, can occur model molecular C - C/C - O bond breaking, to obtain aromatic amide, α - one amide, aromatic acid and phenol compounds. The mild conditions, cheap catalyst and oxidizing agent, various controllable reaction product, the reaction process is simple and easy to operate.
Tert -Butyl nitrite promoted transamidation of secondary amides under metal and catalyst free conditions
Sureshbabu, Popuri,Azeez, Sadaf,Chaudhary, Priyanka,Kandasamy, Jeyakumar
, p. 845 - 850 (2019/01/30)
A mild and efficient method is demonstrated for the transamidation of secondary amides with various amines including primary, secondary, cyclic and acyclic amines in the presence of tert-butyl nitrite. The reaction proceeds through the N-nitrosamide intermediate and provides the transamidation products in good to excellent yields at room temperature. Moreover, the developed methodology does not require any catalyst or additives.
Visible-Light-Driven Oxidation of N -Alkylamides to Imides Using Oxone/H 2 O and Catalytic KBr
Mei, Chong,Hu, Yixin,Lu, Wenjun
supporting information, p. 2999 - 3005 (2018/05/25)
Imides are prepared conveniently by visible-light-driven oxidations of various N -alkylamides under mild conditions. The majority of the reactions proceed efficiently by using Oxone as the oxidant in the presence of a catalytic amount of KBr in H 2 O/CH 2 Cl 2 under irradiation by an 8 W white LED at room temperature. Experimental studies suggest that an imine, obtained from the substrate amide via a radical process, is the key intermediate.
