408531-60-2Relevant academic research and scientific papers
Cooperative Catalytic Activation of Si?H Bonds: CO2-Based Synthesis of Formamides from Amines and Hydrosilanes under Mild Conditions
Luo, Rongchang,Lin, Xiaowei,Chen, Yaju,Zhang, Wuying,Zhou, Xiantai,Ji, Hongbing
, p. 1224 - 1232 (2017)
A simple cooperative catalytic system was successfully developed for the solvent-free N-formylation of amines with CO2 and hydrosilanes under ambient conditions, which was composed of a Zn(salen) catalyst and quaternary ammonium salt. These commercially available binary components activated the Si?H bonds effectively, owing to the intermolecular synergistic effect between Lewis base and transition metal center (LB–TM), and subsequently facilitated the insertion of CO2 to form the active silyl formats, thereby leading to excellent catalytic performance at a low catalyst loading. Furthermore, the bifunctional Zn(salen) complexes, with two imidazolium-based ionic-liquid (IL) units at the 3,3′-position of salen ligand, acted as intramolecularly cooperative catalysts, and the solvent-regulated separation resulted in facile catalyst recycling and reuse.
Lewis Base Promoted Reduction of CO2 with BH3NH3 into Boryl Formates: CO2 as a Carbon Source in Organic Synthesis Under Mild Conditions
Zhang, Bo,Du, Gaixia,Hang, Wei,Wang, Sheng,Xi, Chanjuan
supporting information, p. 1739 - 1743 (2018/04/24)
Lewis base promoted selective reduction of CO2 into boryl formates by using BH3NH3 as a reductant under mild conditions has been reported. The boryl formates, generated in situ, were shown to be reactive and versatile sources of formyl compounds to create new C–N, C–O, and C–C bonds. The reactivity of the boryl formates to yield formic acid, formamides, formates, secondary alcohols, and benzoheterocyclic rings was investigated.
Selective formylation and methylation of amines using carbon dioxide and hydrosilane catalyzed by alkali-Metal carbonates
Fang, Chi,Lu, Chunlei,Liu, Muhua,Zhu, Yiling,Fu, Yao,Lin, Bo-Lin
, p. 7876 - 7881 (2018/05/23)
The formylation and methylation of amines with carbon dioxide and hydrosilanes are emerging yet important types of transformations for CO2. Catalytic methods effective for both reactions with wide substrate scopes are rare because of the difficulty in controlling the selectivity. Herein, we report that simple and readily available inorganic bases alkali-metal carbonates, especially cesium carbonatecatalyze both the formylation and methylation reactions efficiently under mild conditions. The selectivity can be conveniently controlled by varying the reaction temperature and silane. A “cesium effect” on both reactions was observed by comparing the catalytic activity of various alkali-metal carbonates. Combined experimental and computational studies suggested the following reaction mechanism: (i) activation of Si?H by Cs2CO3, (ii) insertion of CO2 into Si?H, (iii) formylation of amines by silyl formate, and (iv) reduction of formamides to methylamines.
Carbon Dioxide Based N-Formylation of Amines Catalyzed by Fluoride and Hydroxide Anions
Hulla, Martin,Bobbink, Felix D.,Das, Shoubhik,Dyson, Paul J.
, p. 3338 - 3342 (2016/11/16)
We described herein a simple approach for N-formylation with CO2 and hydrosilane reducing agents. Fluoride and hydroxide salts efficiently catalyzed the reaction, principally through activation of the hydrosilanes, which led to hydrosilane reactivities comparable to those of NaBH4/LiAlH4. Consequently, the N-formylation of amines with CO2 could be achieved at room temperature and atmospheric pressure. The mechanism of these anionic catalysts contrasts that of the currently reported systems, for which activation of CO2 is the key mechanistic step. Using tetrabutylammonium fluoride as a simple ammonium salt catalyst, the N-formylated products of both aliphatic and aromatic amines could be obtained in excellent yields with high selectivities.
Method for Preparing Formamide Compounds
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Paragraph 0126-0136, (2014/02/16)
The present invention relates to a method for preparing formamide compounds using carbon dioxide, and to the use of said method for manufacturing vitamins, pharmaceutical products, adhesives, acrylic fibres, synthetic leathers, pesticides and fertilisers. The invention also relates to a method for manufacturing vitamins, pharmaceutical products, adhesives, acrylic fibres, synthetic leathers, pesticides and fertilisers which includes a step of preparing formamide compounds by the method according to the invention.
Recycling of carbon and silicon wastes: Room temperature formylation of N-H bonds using carbon dioxide and polymethylhydrosiloxane
Jacquet, Olivier,Das Neves Gomes, Christophe,Ephritikhine, Michel,Cantat, Thibault
supporting information; experimental part, p. 2934 - 2937 (2012/03/27)
A highly active organocatalytic system based on N-heterocyclic carbenes has been designed for the formylation of N-H bonds in a large variety of nitrogen molecules and heterocycles, using two chemical wastes: CO2 and polymethylhydrosiloxane (PMHS).
