- Evidence for Silica Surface Three- And Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts
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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.
- 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.
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- Reusable Co-nanoparticles for general and selectiveN-alkylation of amines and ammonia with alcohols
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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.
- Beller, Matthias,Gawande, Manoj B.,Jagadeesh, Rajenahally V.,Kadam, Ravishankar G.,Li, Xinmin,Ma, Zhuang,Petr, Martin,Zbo?il, Radek,Zhou, Bei
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p. 111 - 117
(2022/01/06)
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- A Selective and General Cobalt-Catalyzed Hydroaminomethylation of Olefins to Amines
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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
- Beller, Matthias,Delolo, Fábio G.,Jackstell, Ralf,Spannenberg, Anke,Yang, Ji
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supporting information
(2021/12/06)
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- Method for synthesizing heteroatom- substituted aromatic compound from styrene compound
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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.
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Paragraph 0248-0251
(2021/02/06)
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- Linear Hydroaminoalkylation Products from Alkyl-Substituted Alkenes
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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.
- Warsitz, Michael,Doye, Sven
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supporting information
p. 15121 - 15125
(2020/10/23)
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- C–N Cross-coupling Reactions of Amines with Aryl Halides Using Amide-Based Pincer Nickel(II) Catalyst
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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.
- Albkuri, Yahya M.,RanguMagar, Ambar B.,Brandt, Andrew,Wayland, Hunter A.,Chhetri, Bijay P.,Parnell, Charlette M.,Szwedo, Peter,Parameswaran-Thankam, Anil,Ghosh, Anindya
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p. 1669 - 1678
(2019/12/27)
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- Alkylation of Amines Via Tandem Hydroaminomethylation Using Imino-Pyridine Complexes of Rhodium as Catalyst Precursors
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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
- October, Jacquin,Mapolie, Selwyn F.
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p. 998 - 1010
(2019/11/03)
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- Electrochemically Oxidative C-C Bond Cleavage of Alkylarenes for Anilines Synthesis
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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
- Adeli, Yeerlan,Huang, Kaimeng,Liang, Yujie,Jiang, Yangye,Liu, Jianzhong,Song, Song,Zeng, Cheng-Chu,Jiao, Ning
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p. 2063 - 2067
(2019/03/12)
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- Regiospecific N-Arylation of Aliphatic Amines under Mild and Metal-Free Reaction Conditions
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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.
- Purkait, Nibadita,Kervefors, Gabriella,Linde, Erika,Olofsson, Berit
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p. 11427 - 11431
(2018/08/28)
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- Titanium Catalysts with Linked Indenyl-Amido Ligands for Hydroamination and Hydroaminoalkylation Reactions
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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.
- Rohjans, Stefan H.,Ross, Jan H.,Lühning, Lars H.,Sklorz, Lukas,Schmidtmann, Marc,Doye, Sven
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supporting information
p. 4350 - 4357
(2019/01/03)
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- A 2,6-bis(phenylamino)pyridinato titanium catalyst for the highly regioselective hydroaminoalkylation of styrenes and 1,3-butadienes
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The C-C bond forming catalytic hydroaminoalkylation of terminal alkenes, 1,3-dienes, or styrenes allows a direct and highly atom efficient (100 %) synthesis of amines which can result in the formation of two regioisomers, the linear and the branched product. We present a new titanium catalyst with 2,6-bis(phenylamino)pyridinato ligands for intermolecular hydroaminoalkylation reactions of styrenes and 1-phenyl-1,3-butadienes that delivers the corresponding linear hydroaminoalkylation products with excellent regioselectivities. Linear progress: A new Ti complex with 2,6-bis(phenylamino) pyridinato ligands catalyzes highly regioselective hydroaminoalkylation reactions of styrenes. The process that directly gives access to the corresponding linear hydroaminoalkylation products offers a new and flexible synthetic approach towards pharmaceutically important 3-arylpropylamines. It is also possible to convert (E)-1-phenyl-1,3-butadienes into the corresponding linear products.
- Doerfler, Jaika,Preuss, Till,Schischko, Alexandra,Schmidtmann, Marc,Doye, Sven
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p. 7918 - 7922
(2014/08/05)
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- Phosphine- and hydrogen-free: Highly regioselective ruthenium-catalyzed hydroaminomethylation of olefins
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A highly regioselective ruthenium-catalyzed hydroaminomethylation of olefins is reported. Using easily available trirutheniumdodecacarbonyl an efficient sequence consisting of a water-gas shift reaction, hydroformylation of olefins, with subsequent imine or enamine formation and final reduction is realized. This novel procedure is highly practical (ligand-free, one pot) and economic (low catalyst loading and inexpensive metal). Bulk industrial as well as functionalized olefins react with various amines to give the corresponding tertiary amines generally in high yields (up to 92), excellent regioselectivities (n/iso>99:1), and full chemoselectivity in favor of terminal olefins.
- Gülak, Samet,Wu, Lipeng,Liu, Qiang,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 7320 - 7323
(2014/07/21)
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- Catalytic hydrogenation of amides to amines under mild conditions
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Under (not so much) pressure: A general method for the hydrogenation of tertiary and secondary amides to amines with excellent selectivity using a bimetallic Pd-Re catalyst has been developed. The reaction proceeds under low pressure and comparatively low temperature. This method provides organic chemists with a simple and reliable tool for the synthesis of amines. Copyright
- Stein, Mario,Breit, Bernhard
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supporting information
p. 2231 - 2234
(2013/03/28)
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- Homogeneous catalytic hydrogenation of amides to amines
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Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4-pentanedione), triphos [1,1,1-tris- (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from prepared from [Ru(acac) 3], triphos and MSA, or from reactions of [RuX-(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crys-tallographically characterised complexes include: [Ru(OAc-κ1O) 2(H2O)-(triphos)], [Ru(OAc-κ2O,O') (CH3SO3-κ1O)(triphos)], [Ru(CH 3SO3-κ1O)2-(H 2O)(triphos)] and [Ru2(μ-CH3SO 3)3-(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc-κ1O)(OAc- κ2O,O')(triphos)],[Ru(CH3SO3- κ1O)(CH3SO3-κ2O,O')- (triphos)], H[Ru(CH3SO3-κ1O) 3-(triphos)], [RuH(CH3SO3-κ1O) (CO)-(triphos)] and [RuH(CH3SO3-k2O,O')- (triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.
- Coetzee, Jacorien,Dodds, Deborah L.,Klankermayer, Jürgen,Brosinski, Sandra,Leitner, Walter,Slawin, Alexandra M. Z.,Cole-Hamilton, David J.
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supporting information
p. 11039 - 11050
(2013/09/02)
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- Aminopyridinato titanium catalysts for the hydroaminoalkylation of alkenes and styrenes
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The linear product is formed as the major product when in situ generated titanium complexes with aminopyridinato ligands are used as catalysts for hydroaminoalkylation reactions of styrenes (see scheme). The reaction is not limited to the use of N-methyla
- Doerfler, Jaika,Doye, Sven
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supporting information
p. 1806 - 1809
(2013/04/10)
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- FeCl2-promoted cleavage of the unactivated C-C bond of alkylarenes and polystyrene: Direct synthesis of arylamines
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Ironing it out: An efficient and convenient nitrogenation strategy involving C-C bond cleavage for the straightforward synthesis of versatile arylamines is presented. Various alkyl azides and alkylarenes, including the common industrial by-product cumene, react using this protocol. Moreover, this method provides a potential strategy for the degradation of polystyrene. Copyright
- Qin, Chong,Shen, Tao,Tang, Conghui,Jiao, Ning
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supporting information; experimental part
p. 6971 - 6975
(2012/09/25)
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- Titanium-catalyzed hydroaminoalkylation of alkenes by C-H bond activation at sp3 centers in the α-position to a nitrogen atom
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(Chemical Equation Presented) Good for primary and secondary amines: Hydroaminoalkylations of alkenes, which take place by C-H bond activation in the α-position to nitrogen atoms, are catalyzed by various neutral titanium complexes (see scheme). Primary a
- Kubiak, Raphael,Prochnow, Insa,Doye, Sven
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supporting information; experimental part
p. 1153 - 1156
(2009/06/19)
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- PRODUCTION OF AMINES
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A process for the hydrogenation of carboxylic acids and/or derivatives, particularly amides, is described. The process includes reacting an acid or derivative such as an amide with a source of hydrogen in the presence of a catalyst system. The catalyst system obtainable by combining: (a) a source of ruthenium, and (b) a phosphine compound of general Formula I: (Formula I). The hydrogenation reaction is carried out in the presence of a low concentration of water or at low pressure or in the presence of a source of ammonia or the hydrogenation reaction is carried out in the absence of water or a combination of these factors is utilised. The invention also relates to the use of ammonia in the production of primary amines by hydrogenation of carboxylic acids and/or derivatives thereof or a process for the production of primary amines generally.
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Page/Page column 18-19
(2008/06/13)
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- The synthesis of amines by the homogeneous hydrogenation of secondary and primary amides
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Amides can be hydrogenated to amines using a catalyst prepared in situ from [Ru(acac)3] and 1,1,1-tris(diphenylphosphinomethyl)ethane; water is required to stabilize the catalyst and primary amines can only be formed (selectivity up to 85%) if ammonia is also present. The Royal Society of Chemistry.
- Nú?ez Magro, Angel A.,Eastham, Graham R.,Cole-Hamilton, David J.
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p. 3154 - 3156
(2008/02/13)
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- The Conversion of Secondary into Tertiary Amides Using Benzotriazole Methodology
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N-Alkyl-N-amides, easily prepared from benzotriazole, an aldehyde, and a secondary amide, react readily with organozinc reagents to give tertiary amides in moderate to good yields.They are also reduced by LiAlH4 to afford tertiary amines.
- Katritzky, Alan R.,Yao, Guowei,Lan, Xiangfu,Zhao, Xiaohong
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p. 2086 - 2093
(2007/10/02)
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