2933-53-1Relevant articles and documents
Ru-Catalyzed Switchable N-Hydroxyethylation and N-Acetonylation with Crude Glycerol
Xin, Zhuo,Jia, Le,Huang, Yuxing,Du, Chen-Xia,Li, Yuehui
, p. 2007 - 2011 (2020/03/19)
Highly efficient Ru-catalyzed selective C?C or C?O bond cleavage of polyols (e.g., crude glycerol) for N-hydroxyethylation or N-acetonylation of amines was achieved through the hydrogen-borrowing approach. A variety of amines were transformed to the desired amino alcohols/ketones in moderate-to-excellent yields, opening up new avenues for generation of oxygenated pharmaceuticals and fine chemicals from renewable raw materials. The use of new redox-active catalysts containing bisphosphine/thienylmethylamine ligands allows this hydrogen-borrowing system to be operated selectively under both basic and acidic conditions.
Palladium-catalyzed intramolecular carbene insertion into C(sp3)-H bonds
Solé, Daniel,Mariani, Francesco,Bennasar, M.-Llu?sa,Fernández, Israel
supporting information, p. 6467 - 6470 (2016/06/01)
A palladium-catalyzed carbene insertion into C(sp3)-H bonds leading to pyrrolidines was developed. The coupling reaction can be catalyzed by both Pd0 and PdII, is regioselective, and shows a broad functional group tolerance. This reaction is the first example of palladium-catalyzed C(sp3)-C(sp3) bond assembly starting from diazocarbonyl compounds. DFT calculations revealed that this direct C(sp3)-H bond functionalization reaction involves an unprecedented concerted metalation-deprotonation step. Pd in action: Palladium has been used to catalyze the C(sp3)-H insertion of metal carbenoids derived from α-diazoesters to form pyrrolidines through intramolecular assembly of C(sp3)-C(sp3) bonds. A reaction mechanism involving a metalation-deprotonation step instead of the usual concerted but asynchronous process is proposed.