33967-18-9Relevant articles and documents
Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents: A Direct Approach to Anilines?
Qiu, Xu,Wang, Yachong,Su, Lingyu,Jin, Rui,Song, Song,Qin, Qixue,Li, Junhua,Zong, Baoning,Jiao, Ning
supporting information, p. 3011 - 3016 (2021/09/13)
Amines are among the most fundamental motifs in chemical synthesis, and the introduction of amine building blocks via selective C—C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification. Herein, we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents, which are easily prepared from hydroxylamine. Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions. Good compatibility and valuable applications of the transformation were also displayed.
Pyridine mediated transition-metal-free direct alkylation of anilines using alcohols: via borrowing hydrogen conditions
Pothikumar, Rajagopal,Bhat, Venugopal T,Namitharan, Kayambu
supporting information, p. 13607 - 13610 (2020/11/17)
Herein, we report pyridine and other similar azaaromatics as efficient biomimetic hydrogen shuttles for a transition-metal-free direct N-alkylation of aryl and heteroaryl amines using a variety of benzylic and straight chain alcohols. Mechanistic studies including deuterium labeling and the isolation of dihydro-intermediates of the benzannulated pyridine confirmed the role of pyridine and a borrowing hydrogen process operating in these reactions. In addition, we have extended this methodology for the development of dehydrogenative synthesis of quinolines and indoles, as well as the transfer hydrogenation of ketones. This journal is
Transfer Hydrogenation of Ketones and Imines with Methanol under Base-Free Conditions Catalyzed by an Anionic Metal-Ligand Bifunctional Iridium Catalyst
Han, Xingyou,Li, Feng,Liu, Peng,Wang, Rongzhou,Xu, Jing
, p. 2242 - 2249 (2020/03/13)
An anionic iridium complex [Cp*Ir(2,2′-bpyO)(OH)][Na] was found to be a general and highly efficient catalyst for transfer hydrogenation of ketones and imines with methanol under base-free conditions. Readily reducible or labile substituents, such as nitro, cyano, and ester groups, were tolerated under present reaction conditions. Notably, this study exhibits the unique potential of anionic metal-ligand bifunctional iridium catalysts for transfer hydrogenation with methanol as a hydrogen source.
Method for synthesizing aromatic ketone by catalytic oxidation of aromatic benzylic secondary C-H bonds through metalloporphyrin (by machine translation)
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Paragraph 0082-0083, (2020/09/20)
A method for synthesizing aromatic ketone by catalytic oxidation of aromatic benzylic secondary C-H bonds through metalloporphyrin, the method comprising: (1 ×10) preparing metalloporphyrin-4 % - 1%, Mol / mol are dispersed in the aromatic hydrocarbon, the reaction system is sealed, the temperature is raised to 80 - 150 °C by stirring, the oxidant is introduced to 0.20 - 2.0 mpa, the set temperature and pressure are maintained, ?datdatdate? is stirred 3.0-24 . 0h, and the reaction liquid is subjected to post-treatment to obtain the product aromatic ketone compound. The method has the advantages of low reaction temperature, low catalyst consumption, high selectivity of the aromatic ketone compound, low peroxide content and high production safety factor, and has the potential of overcoming the defects of high reaction temperature, low corrosive solvent and auxiliary agent in the catalytic oxidation process of the aromatic benzylic secondary C-H bonds in the industry. The method is efficient, feasible and safe. (by machine translation)
Method for synthesizing secondary alcohol
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Paragraph 0040; 0041; 0042; 0043, (2019/03/15)
The invention discloses a method for synthesizing secondary alcohol, which utilizes transition metal catalysis and uses isopropanol as a hydrogen source to synthesize the secondary alcohol. The reaction not only uses inexpensive and environmentally friendly isopropanol as the hydrogen source and a solvent, but also has the advantages of high yield, environmental protection, and the like, and therefore the reaction has broad development prospects.
Mild palladium-catalysed highly efficient hydrogenation of CN, C-NO2, and CO bonds using H2 of 1 atm in H2O
Liu, Yaxu,He, Shaopo,Quan, Ziyi,Cai, Huizhuo,Zhao, Yang,Wang, Bo
supporting information, p. 830 - 838 (2019/02/27)
Here we present the first example of a mild and high-efficiency protocol enabling a process in water using 1 atm of H2 for the efficient and selective hydrogenation of nitriles, nitro compounds, ketones, and aldehydes to yield primary amines and alcohols with satisfactory yields of up to >99%. Several palladium-based nanoparticle catalysts were prepared from K2PdCl4 and ligands, and one of them was found to be the best and most suitable for the hydrogenation of CN, C-NO2, and CO bonds. In addition, the catalyst Pd-NPs can be easily recycled and reused without losing their activity and selectivity. A plausible mechanism for the hydrogenation of a CN bond was also proposed, representing the first example that possesses great potential for sustainable industrial purposes.
Half-sandwich Ru (II) complexes containing (N, O) Schiff base ligands: Catalysts for base-free transfer hydrogenation of ketones
Satheesh,Sathish Kumar, Pushpanathan N.,Kumara, P. Raghavendra,Karvembu, Ramasamy,Hosamani, Amar,Nethaji
, (2019/08/07)
Two new half-sandwich Ru (II)(p-cymene) complexes (1 and 2) containing dopamine-based (N, O) Schiff base ligands (L1H and L2H) were synthesized and characterized by FT-IR, UV–Visible and 1H & 13C NMR spectral techniques, and elemental analyses. The spectroscopic and analytical data revealed monobasic bidentate coordination of the ligands with Ru ion. The molecular structures of L1H, L2H and 2 were further confirmed by single crystal X-ray diffraction study. Complexes 1 and 2?have been employed as catalysts in the transfer hydrogenation of ketones using 2-propanol as a hydrogen source at 85?°C under base-free condition. Good to the excellent yield of secondary alcohols, gram scale synthesis, and high TON and TOF made this catalytic system interesting.
Molecular Defined Molybdenum-Pincer Complexes and Their Application in Catalytic Hydrogenations
Leischner, Thomas,Spannenberg, Anke,Junge, Kathrin,Beller, Matthias
supporting information, p. 4402 - 4408 (2019/01/03)
A family of low-valent molybdenum complexes, supported by the pincer ligand (iPr2PCH2CH2)2NH, was prepared and characterized. After activation by NaBHEt3 coordination compounds 2 and 3-Cl were found to be suitable catalysts for the hydrogenation of ketones and olefins.
Transformation of Alkynes into Chiral Alcohols via TfOH-Catalyzed Hydration and Ru-Catalyzed Tandem Asymmetric Hydrogenation
Liu, Sensheng,Liu, Huan,Zhou, Haifeng,Liu, Qixing,Lv, Jinliang
supporting information, p. 1110 - 1113 (2018/02/23)
A novel full atom-economic process for the transformation of alkynes into chiral alcohols by TfOH-catalyzed hydration coupled with Ru-catalyzed tandem asymmetric hydrogenation in TFE under simple conditions has been developed. A range of chiral alcohols was obtained with broad functional group tolerance, good yields, and excellent stereoselectivities.
FLP-Catalyzed Transfer Hydrogenation of Silyl Enol Ethers
Khan, Imtiaz,Reed-Berendt, Benjamin G.,Melen, Rebecca L.,Morrill, Louis C.
, p. 12356 - 12359 (2018/09/18)
Herein we report the first catalytic transfer hydrogenation of silyl enol ethers. This metal free approach employs tris(pentafluorophenyl)borane and 2,2,6,6-tetramethylpiperidine (TMP) as a commercially available FLP catalyst system and naturally occurring γ-terpinene as a dihydrogen surrogate. A variety of silyl enol ethers undergo efficient hydrogenation, with the reduced products isolated in excellent yields (29 examples, 82 % average yield).
