36939-29-4Relevant 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.
A simple iridicycle catalyst for efficient transfer hydrogenation of n-heterocycles in water
Talwar, Dinesh,Li, Ho Yin,Durham, Emma,Xiao, Jianliang
supporting information, p. 5370 - 5379 (2015/03/30)
A cyclometalated iridium complex is shown to catalyse the transfer hydrogenation of various nitrogen heterocycles, including but not limited to quinolines, isoquinolines, indoles and pyridinium salts, in an aqueous solution of HCO2H/HCO2Na under mild conditions. The catalyst shows excellent functional-group compatibility and high turnover number (up to 7500), with catalyst loadings as low as 0.01 mol % being feasible. Mechanistic investigation of the quinoline reduction suggests that the transfer hydrogenation proceeds via both 1,2- and 1,4-addition pathways, with the catalytic turnover being limited by the step of hydride transfer. An easily accessible iridicycle catalyst effects the transfer hydrogenation of a wide variety of N-heterocycles in water, including quinolines, isoquinolines, indoles, quinoxalines, and pyridines. The catalyst shows excellent functional-group compatibility and high turnover number (up to 7500), even with low catalyst loadings.
Efficient and chemoselective reduction of pyridines to tetrahydropyridines and piperidines via rhodium-catalyzed transfer hydrogenation
Wu, Jianjun,Tang, Weijun,Pettman, Alan,Xiao, Jianliang
supporting information, p. 35 - 40 (2013/03/13)
Promoted by iodide anion the rhodium complex dimer, [Cp RhCl 2]2, catalyzes efficiently the transfer hydrogenation of various quaternary pyridinium salts under mild conditions, affording not only piperidines but also 1,2,3,6-tetrahydropyridines in a highly chemoselective fashion, depending on the substitution pattern at the pyridinium ring. The reduction is conducted in azeotropic formic acid/triethylamine (HCOOH-Et 3N) mixture at 40 °C, with catalyst loadings as low as 0.005mol% being feasible. Copyright