3007-72-5Relevant academic research and scientific papers
Evidence for Silica Surface Three- And Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts
Abou-Hamad, Edy,Al Maksoud, Walid,Al-Harbi, Manal S.,Aljuhani, Maha A.,Basset, Jean-Marie,Cavallo, Luigi,El Eter, Mohamad,Jedidi, Abdesslem,Pelletier, Jérémie D. A.,Wackerow, Wiebke,Yaacoub, Layal F.
, (2020)
The single-site silica-supported group IV metal amido complex [Ti(NMe2)4] gives the tris(amido)-supported fragment [(Si-O-)Ti(-NMe2)3], which transforms into a three-membered metallacycle (called a metallaaziridine) by an α-H transfer between two amido ligands. When the three-membered metallacycle reacts with 1-octene, it gives a five-membered metallacycle by insertion of the double bond into the M-C bond of the metallaziridine. These two metallacycles, key intermediates in the catalytic cycle of the hydroaminoalkylation of terminal olefins, were isolated and fully characterized following the surface organometallic chemistry (SOMC) concept and procedures. This paper shows that surface organometallic chemistry can be used to identify and fully characterize three- and five-membered metallacycles of Ti in the hydroaminoalkylation of olefins.
Reusable Co-nanoparticles for general and selectiveN-alkylation of amines and ammonia with alcohols
Beller, Matthias,Gawande, Manoj B.,Jagadeesh, Rajenahally V.,Kadam, Ravishankar G.,Li, Xinmin,Ma, Zhuang,Petr, Martin,Zbo?il, Radek,Zhou, Bei
, p. 111 - 117 (2022/01/06)
A general cobalt-catalyzedN-alkylation of amines with alcohols by borrowing hydrogen methodology to prepare different kinds of amines is reported. The optimal catalyst for this transformation is prepared by pyrolysis of a specific templated material, which is generatedin situby mixing cobalt salts, nitrogen ligands and colloidal silica, and subsequent removal of silica. Applying this novel Co-nanoparticle-based material, >100 primary, secondary, and tertiary amines includingN-methylamines and selected drug molecules were conveniently prepared starting from inexpensive and easily accessible alcohols and amines or ammonia.
A Selective and General Cobalt-Catalyzed Hydroaminomethylation of Olefins to Amines
Beller, Matthias,Delolo, Fábio G.,Jackstell, Ralf,Spannenberg, Anke,Yang, Ji
supporting information, (2021/12/06)
A new cobalt catalyst is presented for the domino hydroformylation-reductive amination reaction of olefins. The optimal Co-tert-BuPy-Xantphos catalyst shows good to excellent linear-to-branched (n/iso) regioselectivity for the reactions of aliphatic alken
Method for synthesizing heteroatom- substituted aromatic compound from styrene compound
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Paragraph 0248-0251, (2021/02/06)
The invention discloses a method for synthesizing a heteroatom-substituted aromatic compound from a styrene compound, which comprises the following steps of: mixing a styrene compound with a general formula (I) and a heteroatom-containing compound with a general formula (II), and reacting in the presence of an acid additive and an organic solvent to obtain a heteroatom-substituted compound with ageneral formula (III). According to the synthesis method disclosed by the invention, a large amount of styrene compounds are used as raw materials and react to generate aromatic amine or phenol compounds under the action of no metal catalysis; and compared with the traditional aromatic amine and phenol synthesis method, the method has the advantages of high yield, simple conditions, low waste discharge amount, no metal participation, simple reaction equipment, easiness in industrial production and the like.
Linear Hydroaminoalkylation Products from Alkyl-Substituted Alkenes
Warsitz, Michael,Doye, Sven
supporting information, p. 15121 - 15125 (2020/10/23)
The regioselective conversion of alkyl-substituted alkenes into linear hydroaminoalkylation products represents a strongly desirable synthetic transformation. In particular, such conversions of N-methylamine derivatives are of great scientific interest, because they would give direct access to important amines with unbranched alkyl chains. Herein, we present a new one-pot procedure that includes an initial alkene hydroaminoalkylation with an α-silylated amine substrate and a subsequent protodesilylation reaction that delivers linear hydroaminoalkylation products with high selectivity from simple alkyl-substituted alkenes. For that purpose, new titanium catalysts have been developed, which are able to activate the α-C?H bond of more challenging α-silylated amine substrates. In addition, a direct relationship between the ligand structure of the new catalysts and the obtained regioselectivity is described.
C–N Cross-coupling Reactions of Amines with Aryl Halides Using Amide-Based Pincer Nickel(II) Catalyst
Albkuri, Yahya M.,RanguMagar, Ambar B.,Brandt, Andrew,Wayland, Hunter A.,Chhetri, Bijay P.,Parnell, Charlette M.,Szwedo, Peter,Parameswaran-Thankam, Anil,Ghosh, Anindya
, p. 1669 - 1678 (2019/12/27)
Abstract: An approach to C–N cross-coupling reactions of aryl halides with amines in the presence of an amide-based pincer nickel(II) catalyst (2) is described. For 3?h reactions at 110?°C with 0.2?mol% catalyst, aryl bromides gave higher turnover numbers (TON) than the corresponding chlorides or iodides. Both primary and secondary amines could be used with the former giving higher TON. However, sterically hindered amines showed lower TON. In elucidating the mechanism of this nickel complex-catalyzed C–N cross coupling reaction it was found that the rate of reaction was unchanged in the presence of radical quenchers and a plausible Ni(I)–Ni(III) pathway is proposed. Graphic Abstract: [Figure not available: see fulltext.]Nickel pincer catalyst proved to be excellent catalyst for the C-N cross-coupling reaction with the high turnover number (TON) for 1° and 2° amines and different nonactivated aryl halides under optimum conditions.
Alkylation of Amines Via Tandem Hydroaminomethylation Using Imino-Pyridine Complexes of Rhodium as Catalyst Precursors
October, Jacquin,Mapolie, Selwyn F.
, p. 998 - 1010 (2019/11/03)
Abstract: Novel cationic Rh(I) imino-pyridine complexes were evaluated as catalyst precursors in the hydroaminomethylation of 1-octene in conjunction with both primary (aniline and benzylamine) and secondary amines (piperidine). These complexes were found
Electrochemically Oxidative C-C Bond Cleavage of Alkylarenes for Anilines Synthesis
Adeli, Yeerlan,Huang, Kaimeng,Liang, Yujie,Jiang, Yangye,Liu, Jianzhong,Song, Song,Zeng, Cheng-Chu,Jiao, Ning
, p. 2063 - 2067 (2019/03/12)
In contrast to the recent breakthrough in electrochemical C-H aminations, the electrochemically oxidative C-N bond formation through a C-C bond cleavage is rarely studied. This work describes an electrochemical C-C amination of alkylarenes for the efficie
Regiospecific N-Arylation of Aliphatic Amines under Mild and Metal-Free Reaction Conditions
Purkait, Nibadita,Kervefors, Gabriella,Linde, Erika,Olofsson, Berit
, p. 11427 - 11431 (2018/08/28)
A transition metal-free N-arylation of primary and secondary amines with diaryliodonium salts is presented. Both acyclic and cyclic amines are well tolerated, providing a large set of N-alkyl anilines. The methodology is unprecedented among metal-free methods in terms of amine scope, the ability to transfer both electron-withdrawing and electron-donating aryl groups, and efficient use of resources, as excess substrate or reagents are not required.
Titanium Catalysts with Linked Indenyl-Amido Ligands for Hydroamination and Hydroaminoalkylation Reactions
Rohjans, Stefan H.,Ross, Jan H.,Lühning, Lars H.,Sklorz, Lukas,Schmidtmann, Marc,Doye, Sven
supporting information, p. 4350 - 4357 (2019/01/03)
Titanium complexes containing a bridging indenylethylamido ligand have been synthesized and used as catalysts for hydroamination and hydroaminoalkylation reactions. All dichloro titanium complexes (η5:η1-Ind-C2H4-NR)TiCl2 (R = i-Pr (2a), t-Bu (2b), Cy (2c), Ph (2d)), which were prepared by reacting TiCl4(Et2O)2 with Li2[Ind-C2H4-NR], were fully characterized by single-crystal X-ray analysis. Reaction of 2a-c with methyllithium gave the thermally sensitive corresponding dimethyl titanium complexes [η5:η1-Ind-C2H4-N(alkyl)]TiMe2 (alkyl = i-Pr (3a), t-Bu (3b), Cy (3c)), while the N-aryl-substituted dimethyl titanium complexes [η5:η1-Ind-C2H4-N(aryl)]TiMe2 (aryl = Ph (3d), p-MeOC6H4 (3e)) were directly prepared by reacting Li2[Ind-C2H4-N(aryl)] with in situ generated Cl2TiMe2. In the case of complex 3d, the molecular structure could be determined by single-crystal X-ray analysis. All dimethyl titanium complexes (η5:η1-Ind-C2H4-NR)TiMe2 (R = i-Pr (3a), t-Bu (3b), Cy (3c), Ph (3d), p-MeOC6H4 (3e)) were finally used as precatalysts for the intermolecular hydroaminoalkylation of 1-octene (4), the intramolecular hydroamination and hydroaminoalkylation reactions of aminoalkenes, and the intermolecular hydroamination of 1-phenylpropyne (12). These experiments showed that the N substituent of the indenylethylamido ligand strongly influences the activity of the catalysts in the individual reactions.
