5005-72-1Relevant articles and documents
Titanium-Catalyzed Intermolecular Hydroaminoalkylation of Alkenes with Tertiary Amines
Geik, Dennis,Rosien, Michael,Bielefeld, Jens,Schmidtmann, Marc,Doye, Sven
supporting information, p. 9936 - 9940 (2021/03/31)
The first cationic titanium catalyst system for the intermolecular hydroaminoalkylation of alkenes with various tertiary alkylamines is presented. Corresponding reactions which involve the addition of the α-C?H bond of a tertiary amine across the C?C double bond of an alkene take place at temperatures close to room temperature with excellent regioselectivity to deliver the branched products exclusively. Interestingly, for selected amines, α-C?H bond activation occurs not only at N-methyl but also at N-methylene groups.
Iodine-Mediated Coupling of Cyclic Amines with Sulfonyl Hydrazides: an Efficient Synthesis of Vinyl Sulfone Derivatives
Rong, Xiaona,Guo, Jingwen,Hu, Zheqi,Huang, Lehao,Gu, Yugui,Cai, Yuepiao,Liang, Guang,Xia, Qinqin
supporting information, p. 701 - 708 (2020/12/30)
An efficient iodine-mediated coupling of cyclic amines with sulfonyl hydrazides is reported. This transformation opens a new route to the synthesis of vinyl sulfones derivatives, which is a common structural motif in natural products and pharmaceuticals. Tentative mechanistic studies suggest that this reaction is likely to involve a radical process.
Heterogeneous Ru/TiO2for hydroaminomethylation of olefins: multicomponent synthesis of amines
An, Jinghua,Gao, Zhuyan,Wang, Yehong,Zhang, Zhixin,Zhang, Jian,Li, Lu,Tang, Bo,Wang, Feng
supporting information, p. 2722 - 2728 (2021/04/21)
Synthesizing aminesviathe hydroaminomethylation (HAM) reaction of olefins, a multicomponent reaction, has been regarded as one of the most attractive methods compared with the traditional methods considering the atom economy and environmental friendliness. However, the use of homogeneous catalysts, complex ligands containing diphosphine or nitrogen, and base or acid additives has severely hampered the utilization of these methods. Herein, an efficient heterogeneous Ru/TiO2-catalyzed HAM reaction of olefins is developed without any additives. Various amines, including secondary and tertiary amines, can be successfully obtained from olefins including aromatic and aliphatic olefins. Systematic studies demonstrate the lower electron density of Ruδ+and the higher number of acid sites of Ru/TiO2, leading to the high HAM reaction activity of olefins. Most importantly, nitrobenzene derivatives can also be transformed to the corresponding products over Ru/TiO2in excellent yields.
Mild Hydrogenation of Amides to Amines over a Platinum-Vanadium Bimetallic Catalyst
Mitsudome, Takato,Miyagawa, Kazuya,Maeno, Zen,Mizugaki, Tomoo,Jitsukawa, Koichiro,Yamasaki, Jun,Kitagawa, Yasutaka,Kaneda, Kiyotomi
supporting information, p. 9381 - 9385 (2017/08/01)
Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H2 pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H2 and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H2 at 70 °C or 5 bar H2 at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.
Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines
Musacchio, Andrew J.,Lainhart, Brendan C.,Zhang, Xin,Naguib, Saeed G.,Sherwood, Trevor C.,Knowles, Robert R.
, p. 727 - 730 (2017/02/26)
The intermolecular hydroamination of unactivated alkenes with simple dialkyl amines remains an unsolved problem in organic synthesis. We report a catalytic protocol for efficient additions of cyclic and acyclic secondary alkyl amines to a wide range of alkyl olefins with complete anti-Markovnikov regioselectivity. In this process, carbon-nitrogen bond formation proceeds through a key aminium radical cation intermediate that is generated via electron transfer between an excited-state iridium photocatalyst and an amine substrate. These reactions are redox-neutral and completely atom-economical, exhibit broad functional group tolerance, and occur readily at room temperature under visible light irradiation. Certain tertiary amine products generated through this method are formally endergonic relative to their constituent olefin and amine starting materials and thus are not accessible via direct coupling with conventional ground-state catalysts.
From Internal Olefins to Linear Amines: Ruthenium-Catalyzed Domino Water-Gas Shift/Hydroaminomethylation Sequence
Liu, Jie,Kubis, Christoph,Franke, Robert,Jackstell, Ralf,Beller, Matthias
, p. 907 - 912 (2016/02/18)
A selective ruthenium-catalyzed water-gas shift/hydroformylation of internal olefins and olefin mixtures is reported. This novel domino reaction takes place through a catalytic water-gas shift reaction, subsequent olefin isomerization, followed by hydrofo
Mild and selective Et2Zn-catalyzed reduction of tertiary amides under Hydrosilylation conditions
Kovalenko, Oleksandr O.,Volkov, Alexey,Adolfsson, Hans
supporting information, p. 446 - 449 (2015/03/05)
Diethylzinc (Et2Zn) can be used as an efficient and chemoselective catalyst for the reduction of tertiary amides under mild reaction conditions employing cost-effective polymeric silane (PMHS) as the hydride source. Crucial for the catalytic activity was the addition of a substoichiometric amount of lithium chloride to the reaction mixture. A series of amides containing different additional functional groups were reduced to their corresponding amines, and the products were isolated in good-to-excellent yields.
Reusable supported ruthenium catalysts for the alkylation of amines by using primary alcohols
Peishan, Siah,Dang, Tuan Thanh,Seayad, Abdul Majeed,Ramalingam, Balamurugan
, p. 808 - 814 (2014/03/21)
Efficient and recyclable ruthenium catalysts were synthesized from readily available polystyrene-or silica-supported phosphine ligands. Catalysts bound to the polymer support through an ether linkage showed good to excellent activity towards the N-alkylation of primary and secondary amines to afford the alkylated products in 62-99 % yield at 120-140°C. The supported phosphine ligand/ruthenium ratio was found to be crucial for higher catalytic activity and lower ruthenium leaching. The continuous flow N-alkylation of amines was demonstrated by using the supported catalyst in a column reactor. By adopting the hydrogen-borrowing strategy, the synthesis of the anti-Parkinson agent Piribedil was established in 98 % yield at 140°C. Support group steals the show: An efficient Ru-based heterogeneous catalyst from readily available supported phosphine ligands is developed. The nature of the linkage and the extent of ruthenium incorporation are crucial in determining the catalytic activity. The catalyst can be recycled and used under continuous flow in a packed-bed reactor. The alkylation of cyclic amines is achieved in excellent yield at moderate temperatures in the absence of any external base.
Efficient and regioselective ruthenium-catalyzed hydro-aminomethylation of olefins
Wu, Lipeng,Fleischer, Ivana,Jackstell, Ralf,Beller, Matthias
supporting information, p. 3989 - 3996 (2013/04/10)
An efficient and regioselective ruthenium-catalyzed hydroaminomethlyation of olefins is reported. Key to success is the use of specific 2-phosphino-substituted imidazole ligands and triruthenium dodecacarbonyl as catalyst. Both industrially important alip
Zinc-catalyzed reduction of amides: Unprecedented selectivity and functional group tolerance
Das, Shoubhik,Addis, Daniele,Zhou, Shaolin,Junge, Kathrin,Beller, Matthias
supporting information; experimental part, p. 1770 - 1771 (2010/04/25)
(Chemical Equation Presented) A novel zinc-catalyzed reduction of tertiary amides was developed. This system shows remarkable chemoselectivity and substrate scope tolerating ester, ether, nitro, cyano, azo, and keto substituents. Copyright
