15184-98-2Relevant 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.
Heterogeneous Catalyzed Chemoselective Reductive Amination of Halogenated Aromatic Aldehydes
Dumoleijn, Kim N. R.,Villa, Alberto,Marelli, Marcello,Prati, Laura,Moonen, Kristof,Stevens, Christian V.
, p. 3021 - 3026 (2021/05/18)
The chemoselective conversion of a specific functional group in a multifunctional substrate is of great importance in the chemical industry to obtain cost efficient, sustainable and waste free processes. This work focuses on the chemoselective amination of halogenated aromatic aldehydes with dimethyl amine towards halogenated aromatic amines, a raw material used in the production of for example agrochemical active ingredients. It was found that by combining palladium, a metal known for dehalogenation reactions, and copper, known for its direct hydrogenation of aldehydes to alcohols, in one heterogeneous bimetallic catalyst, a synergistic effect is obtained. By depositing copper onto a palladium on carbon catalyst with a Cu/Pd ratio of at least 1 : 1, the yield could be increased from 66 % (Pd/C) to 98 % (PdCu/C). Moreover, this highly active and stable catalyst also showed suppressed dehalogenation side-reactions in several other chemical conversions such as hydrogenation of nitro functional groups and hydrogenation of aldehydes.
Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
, p. 2059 - 2067 (2021/09/02)
Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.