[EN] HYDROGENATION AND DEHYDROGENATION CATALYST, AND METHODS OF MAKING AND USING THE SAME [FR] CATALYSEUR D'HYDROGÉNATION ET DE DÉSHYDROGÉNATION, ET SES PROCÉDÉS DE FABRICATION ET D'UTILISATION
Mild and Selective Cobalt‐Catalyzed Chemodivergent Transfer Hydrogenation of Nitriles
作者:Zhihui Shao、Shaomin Fu、Mufeng Wei、Shaolin Zhou、Qiang Liu
DOI:10.1002/anie.201608345
日期:2016.11.14
Herein, we describe a selective cobalt‐catalyzed chemodivergent transferhydrogenation of nitriles to synthesize primary, secondary, and tertiary amines. The solvent effect plays a key role for the selectivity control. The general applicability of this procedure was highlighted by the synthesis of more than 70 amine products bearing various functional groups in high chemoselectivity. Moreover, this
Cobalt Phosphino-α-Iminopyridine-Catalyzed Hydrofunctionalization of Alkenes: Catalyst Development and Mechanistic Analysis
作者:Wan-Yi Chu、Ryan Gilbert-Wilson、Thomas B. Rauchfuss、Maurice van Gastel、Frank Neese
DOI:10.1021/acs.organomet.6b00457
日期:2016.9.12
A family of CoCl2(PNpy) complexes were prepared, where PNpy = 2-iminopyridyl-phosphine ligands derived from amino-alkyl and aminoaryl phosphines and 2-keto- and 2-formylpyridines. Reduction of CoCl2(PNpy) complexes in the presence of PPh3 gave CoH(PNpy)(PPh3) and CoMe(PNpy)(PPh3), which were active for hydrofunctionalization of alkenes. According to DFT calculations, the CoMe(PNpy)(PPh3) complexes are best described as Co (II) derivatives of the anion [PNpy](-), with a labile PPh3 coligand. Metalation of Na[(Ph2)PC(2)N(H)py] gave the dimers [CoCl2(P(C2)N(H)py)](2). Monomeric complexes catalyze hydrosilylation of 1-octene with Ph2SiH2, with the CoCl2 ((iPr2)P(C3)N(H)py)/2NaBEt(3)H system exhibiting the highest rate and selectivity for anti-Markovnikov product. In situ NMR studies established the following: (i) silanes protonolyze catalyst precursors to give the. Co-silylcomplexes Co (SiR3) ((Ph2)P(C6H4)N(Ph)py)(pph(3)), (ii) alkenes compete with PPh3 to give Co(SiHPh2)((Ph2)P(C6H4)N(Ph)py) (eta(2)-alkene), (iii) ethylene inserts into the Co-Si bond to give Co(CH2CH3SiR3)((Ph2)P(C6H4)N(Ph)py)(pph(3)).
[EN] HYDROGENATION AND DEHYDROGENATION CATALYST, AND METHODS OF MAKING AND USING THE SAME<br/>[FR] CATALYSEUR D'HYDROGÉNATION ET DE DÉSHYDROGÉNATION, ET SES PROCÉDÉS DE FABRICATION ET D'UTILISATION
申请人:GOUSSEV DMITRI
公开号:WO2013023307A1
公开(公告)日:2013-02-21
The present application discloses complexes useful as catalysts for organic chemical synthesis including hydrogenation and dehydrogenation of unsaturated compounds or dehydrogenation of substrates. The range of hydrogenation substrate compounds includes esters, lactones, oils and fats, resulting in alcohols, diols, and triols as reaction products. The catalysts of current application can be used to catalyze a hydrogenation reaction under solvent free conditions. The present catalysts also allow the hydrogenation to proceed without added base, and it can be used in place of the conventional reduction methods employing hydrides of the main-group elements. Furthermore, the catalysts of the present application can catalyze a dehydrogenation reaction under homogenous and/or acceptorless conditions. As such, the catalysts provided herein can be useful in substantially reducing cost and improving the environmental profile of manufacturing processes for variety of chemicals.
[EN] CATALYTIC CONVERSION OF CARBON DIOXIDE TO METHANOL<br/>[FR] CONVERSION CATALYTIQUE DU DIOXYDE DE CARBONE EN MÉTHANOL
申请人:KAMAL PHARMACHEM INC
公开号:WO2019193483A1
公开(公告)日:2019-10-10
The present disclosure relates to a new catalytic process for the production of methanol from carbon dioxide, comprising: (1) the conversion of carbon dioxide and hydrogen to formic acid or formate salts; (2) converting the formic acid or formate salts to diformate esters of diols; (3) hydrogenating the diformate esters to methanol and diols. The diols produced from the hydrogenation reaction can be recovered and re-used to prepare the diformate esters.