205510-63-0Relevant articles and documents
Transition-Metal-Free Reductive Functionalization of Tertiary Carboxamides and Lactams for α-Branched Amine Synthesis
Chiba, Shunsuke,Dixon, Darren J.,Fan, Dongyang,Ong, Derek Yiren
supporting information, p. 11903 - 11907 (2020/05/22)
A new method for the synthesis of α-branched amines by reductive functionalization of tertiary carboxamides and lactams is described. The process relies on the efficient and controlled reduction of tertiary amides by a sodium hydride/sodium iodide composite, in situ treatment of the resulting anionic hemiaminal with trimethylsilyl chloride and subsequent coupling with nucleophilic reagents including Grignard reagents and tetrabutylammonium cyanide. The new method exhibits broad functional-group compatibility, operates under transition-metal-free reaction conditions, and is suitable for various synthetic applications on both sub-millimole and on multigram scales.
Palladium nanoparticles on a pyridinium supported ionic liquid phase: a recyclable and low-leaching palladium catalyst for aminocarbonylation reactions
Adamcsik, Bernadett,Nagy, Enik?,Pekker, Péter,Skoda-F?ldes, Rita,Szabó, Péter,Urbán, Béla
, p. 23988 - 23998 (2020/07/14)
A new SILP (Supported Ionic Liquid Phase) palladium catalyst was prepared and characterized by 13C and 29Si CP MAS NMR, DTG, FTIR and TEM. The presence of the grafted pyridinium cations on the surface of the support was found to result in the formation of highly dispersed Pd nanoparticles with their diameter in the range of 1-2 nm. The catalyst was proved to be active not only in the aminocarbonylation of some model compounds but also in the synthesis of active pharmaceutical ingredients. Catalyst recycling and palladium leaching studies were carried out for the first time in aminocarbonylations leading to CX-546(1-(1,4-benzodioxan-6-ylcarbonyl)piperidine), Moclobemide, Nikethamide and a precursor of Finasteride. The latter reaction proves that not only aryl iodides but also an iodoalkene can be converted into the products with the help of the heterogeneous catalyst. The results show that the conditions should be always fine-tuned in the reactions of different substrates to achieve optimal results. Palladium loss was also observed to depend considerably on the nature of the reaction partners. This journal is
Chloroform as a Carbon Monoxide Precursor: In or Ex Situ Generation of CO for Pd-Catalyzed Aminocarbonylations
Gockel, Samuel N.,Hull, Kami L.
supporting information, p. 3236 - 3239 (2015/07/15)
Conditions for the rapid hydrolysis of chloroform to carbon monoxide (CO) using heterogeneous CsOH·H2O are described. CO and 13CO can be generated cleanly and rapidly under mild conditions and can be captured either in or ex situ in palladium-catalyzed aminocarbonylation reactions. Utilizing only 1-3 equiv of CO allows for the aminocarbonylation of aryl, vinyl, and benzyl halides with a wide variety of primary and secondary amines giving amide products in good to excellent yields. (Chemical Equation Presented).
Palladium nanoparticles supported on ZIF-8 as an efficient heterogeneous catalyst for aminocarbonylation
Dang, Tuan T.,Zhu, Yinghuai,Ngiam, Joyce S. Y.,Ghosh, Subhash C.,Chen, Anqi,Seayad, Abdul M.
, p. 1406 - 1410 (2013/07/26)
Pd nanoparticles supported on ZIF-8 (PdNPs/ZIF-8) are described as an efficient heterogeneous catalyst for the aminocarbonylation of bromoarenes in the presence of phosphines and iodoarenes under phosphine-free conditions. The catalyst can be readily prepared and is air-stable. The palladium loading can be as low as 1 wt %, and the catalyst was recycled four times with negligible change in catalytic performance. A variety of pharmaceutically important amides was readily synthesized. A TON of 2540 was easily achieved in a batch reaction by scaling up to a gram scale. The catalyst reported can also be applied to the synthesis of cyclic and primary amides as well as an alkoxycarbonylation reaction to form an ester.
SYSTEM PROVIDING CONTROLLED DELIVERY OF GASEOUS CO FOR CARBONYLATION REACTIONS
-
Page/Page column 97, (2012/06/30)
A carbonylation system comprising at least one carbon monoxide producing chamber and at least one carbon monoxide consuming chamber forming an interconnected multi-chamber system, said interconnection allowing carbon monoxide to pass from the at least one carbon monoxide producing chamber to the at least one carbon monoxide consuming chamber, said at least one carbon monoxide producing chamber containing a reaction mixture comprising a carbon monoxide precursor and a catalyst, said at least one carbon monoxide consuming chamber being suitable for carbonylation reactions, said interconnected multi- chamber system being sealable from the surrounding atmosphere during carbonylation.
Ex situ generation of stoichiometric and substoichiometric 12CO and 13CO and its efficient incorporation in palladium catalyzed aminocarbonylations
Hermange, Philippe,Lindhardt, Anders T.,Taaning, Rolf H.,Bjerglund, Klaus,Lupp, Daniel,Skrydstrup, Troels
supporting information; experimental part, p. 6061 - 6071 (2011/06/19)
A new technique for the ex situ generation of carbon monoxide (CO) and its efficient incorporation in palladium catalyzed carbonylation reactions was achieved using a simple sealed two-chamber system. The ex situ generation of CO was derived by a palladium catalyzed decarbonylation of tertiary acid chlorides using a catalyst originating from Pd(dba)2 and P(tBu)3. Preliminary studies using pivaloyl chloride as the CO-precursor provided an alternative approach for the aminocarbonylation of 2-pyridyl tosylate derivatives using only 1.5 equiv of CO. Further design of the acid chloride CO-precursor led to the development of a new solid, stable, and easy to handle source of CO for chemical transformations. The synthesis of this CO-precursor also provided an entry point for the late installment of an isotopically carbon-labeled acid chloride for the subsequent release of gaseous [ 13C]CO. In combination with studies aimed toward application of CO as the limiting reagent, this method provided highly efficient palladium catalyzed aminocarbonylations with CO-incorporations up to 96%. The ex situ generated CO and the two-chamber system were tested in the synthesis of several compounds of pharmaceutical interest and all of them were labeled as their [ 13C]carbonyl counterparts in good to excellent yields based on limiting CO. Finally, palladium catalyzed decarbonylation at room temperature also allowed for a successful double carbonylation. This new protocol provides a facile and clean source of gaseous CO, which is safely handled and stored. Furthermore, since the CO is generated ex situ, excellent functional group tolerance is secured in the carbonylation chamber. Finally, CO is only generated and released in minute amounts, hence, eliminating the need for specialized equipment such as CO-detectors and equipment for running high pressure reactions.
