115000-71-0Relevant academic research and scientific papers
Selective hydroaminomethylation of olefins using simple and efficient Rh-phosphinite complex catalyst
Khan, Shoeb R.,Bhanage, Bhalchandra M.
, p. 711 - 715 (2013)
Hydroaminomethylation of various olefins with primary and secondary amines was carried out using a simple and efficient rhodium-phosphinite complex catalyst. The influence of various reaction parameters including the effects of temperature, pressure, catalyst loading, time and solvents has been investigated. The present protocol is general with wider substrate applicability for the synthesis of an important class of aliphatic amines and arylethylamines. High activity and selectivity for amines was achieved with a very good substrate/catalyst molar ratio (turnover number 2500) under mild reaction conditions. Copyright
Anti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines
Miller, David C.,Ganley, Jacob M.,Musacchio, Andrew J.,Sherwood, Trevor C.,Ewing, William R.,Knowles, Robert R.
, p. 16590 - 16594 (2019/11/03)
We report here a photocatalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated olefins with primary alkyl amines to selectively furnish secondary amine products. These reactions proceed through aminium radical cation (ARC) intermediates and occur at room temperature under visible light irradiation in the presence of an iridium photocatalyst and an aryl thiol hydrogen atom donor. Despite the presence of excess olefin, high selectivities are observed for secondary over tertiary amine products, even though the secondary amines are established substrates for ARC-based olefin amination under similar conditions.
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.
Rhodium exchanged ETS-10 and ETS-4: Efficient heterogeneous catalyst for hydroaminomethylation
Sudheesh,Shukla, Ram S.
, p. 116 - 124 (2014/02/14)
Rhodium exchanged titanosilicates (ETS-10 and ETS-4) were synthesized and found to be efficient and stable catalysts for hydroaminomethylation reaction. The catalyst was highly active and selective towards amine product within lower reaction time of 4 h. 1-Hexene and pyrrolidine were taken as representative substrates for parametric variations using Rh-ETS-10. The increase in pyrrolidine ratio gave some significant information showing a decrease in conversion with increased selectivity. The reason may be the competition between pyrrolidine and 1-hexene for coordination sites in rhodium and which prevents the beta-hydride elimination. The ratios of H2 and CO have influenced hydroaminomethylation and the best performance was in the CO:H2 ratio of 1:4 under the studied conditions. The initial rate of formation of amine was double than that of isomerization of 1-hexene. The Rh cluster like complex was formed on treating the catalyst with syn gas. A homogenous- heterogeneous dual nature of Rh was found during hydroaminomethylation. The catalyst was effectively recycled for three times without much loss in its activity and selectivity.
Rhodium complex encapsulated functionalized hexagonal mesoporous silica for heterogeneous hydroaminomethylation
Sudheesh,Shukla, Ram S.
, p. 159 - 166 (2013/03/28)
HRh(CO)(PPh3)3 complex was encapsulated into the pores of amino functionalized hexagonal mesoporous silica. The catalyst was characterized by physico-chemical techniques like P-XRD, 31P-CPMAS NMR, FT-IR, SEM, ICP and N2 adsorption analysis. The catalyst was active for hydroaminomethylation and a variety of alkenes and amines were used as reactants for hydroaminomethylation. The catalyst afforded to achieve 100% conversion with high (>95%) selectivity to corresponding amines. Parametric variations were performed by taking 1-hexene and morpholine as representative reactants for the study of catalyst amount, temperature, pressure and 1-hexene:morpholine ratio. Significant amounts of aldehydes and enamines were observed during the course of the reaction indicating that there could be two possible rate determining steps. The catalyst was effectively recycled up to five times without much loss in its activity and selectivity.
