59507-44-7Relevant articles and documents
Chemoselective Reduction of Tertiary Amides by 1,3-Diphenyl disiloxane (DPDS)
Aldrich, Courtney C.,Hammerstad, Travis A.,Hegde, Pooja V.,Wang, Kathleen J.
, (2022/02/10)
A convenient procedure for the chemoselective reduction of tertiary amides at room temperature in the presence of air and moisture using 1,3-diphenyldisiloxane (DPDS) is developed. The reaction conditions tolerate a significant number of functional groups including esters, nitriles, secondary amides, carbamates, sulfoxides, sulfones, sulfonyl fluorides, halogens, aryl-nitro groups, and arylamines. The conditions reported are the mildest to date and utilize EtOAc, a preferred solvent given its excellent safety profile and lower environmental impact. The ease of setup and broad chemoselectivity make this method attractive for organic synthesis, and the results further demonstrate the utility of DPDS as a selective reducing agent.
Synthesis of the Kinase Inhibitors Nintedanib, Hesperadin, and Their Analogues Using the Eschenmoser Coupling Reaction
Hanusek, Ji?í,Marek, Luká?,Svoboda, Jan,Váňa, Ji?í
, p. 10621 - 10629 (2021/07/31)
A novel synthetic approach involving an Eschenmoser coupling reaction of substituted 3-bromooxindoles (H, 6-Cl, 6-COOMe, 5-NO2) with two substituted thiobenzanilides in dimethylformamide or acetonitrile was used for the synthesis of eight kinase inhibitor
La[N(sime3)2]3-catalyzed deoxygenative reduction of amides with pinacolborane. scope and mechanism
Barger, Christopher J.,Dicken, Rachel D.,Weidner, Victoria L.,Motta, Alessandro,Lohr, Tracy L.,Marks, Tobin J.
supporting information, p. 8019 - 8028 (2020/05/27)
Tris[N,N-bis(trimethylsilyl)amide]lanthanum (LaNTMS) is an efficient and selective homogeneous catalyst for the deoxygenative reduction of tertiary and secondary amides with pinacolborane (HBpin) at mild temperatures (25-60 °C). The reaction, which yields amines and O(Bpin)2, tolerates nitro, halide, and amino functional groups well, and this amide reduction is completely selective, with the exclusion of both competing inter- and intramolecular alkene/alkyne hydroboration. Kinetic studies indicate that amide reduction obeys an unusual mixed-order rate law which is proposed to originate from saturation of the catalyst complex with HBpin. Kinetic and thermodynamic studies, isotopic labeling, and DFT calculations using energetic span analysis suggest the role of a [(Me3Si)2N]2La-OCHR(NR′2)[HBpin] active catalyst, and hydride transfer is proposed to be ligand-centered. These results add to the growing list of transformations that commercially available LaNTMS is competent to catalyze, further underscoring the value and versatility of lanthanide complexes in homogeneous catalysis.
