53179-04-7Relevant articles and documents
A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
Chatterjee, Basujit,Jena, Soumyashree,Chugh, Vishal,Weyhermüller, Thomas,Werlé, Christophe
, p. 7176 - 7185 (2021/06/30)
The direct synthesis of amides and nitriles from readily available aldehyde precursors provides access to functional groups of major synthetic utility. To date, most reliable catalytic methods have typically been optimized to supply one product exclusively. Herein, we describe an approach centered on an operationally simple iron-based system that, depending on the reaction conditions, selectively addresses either the C=O or C-H bond of aldehydes. This way, two divergent reaction pathways can be opened to furnish both products in high yields and selectivities under mild reaction conditions. The catalyst system takes advantage of iron's dual reactivity capable of acting as (1) a Lewis acid and (2) a nitrene transfer platform to govern the aldehyde building block. The present transformation offers a rare control over the selectivity on the basis of the iron system's ionic nature. This approach expands the repertoire of protocols for amide and nitrile synthesis and shows that fine adjustments of the catalyst system's molecular environment can supply control over bond activation processes, thus providing easy access to various products from primary building blocks.
Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
Utsumi, Tatsuki,Noda, Kenta,Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
supporting information, p. 3583 - 3588 (2020/08/05)
Herein, a Grubbs-catalyzed route for the synthesis of nitriles via the aerobic oxidation of primary amines is reported. This reaction accommodates a variety of substrates, including simple primary amines, sterically hindered β,β-disubstituted amines, allylamine, benzylamines, and α-amino esters. Reaction compatibility with various functionalities is also noted, particularly with alkenes, alkynes, halogens, esters, silyl ethers, and free hydroxyl groups. The nitriles were also synthesized via the oxidation of imines generated from aldehydes and NH4OAc in situ. (Figure presented.).
Triphenylbismuth Dichloride-Mediated Conversion of Thioamides to Nitriles
Gopi, Elumalai,Gravel, Edmond,Doris, Eric
supporting information, p. 4043 - 4045 (2019/06/24)
Thioamides were efficiently converted to nitriles using the pentavalent triphenylbismuth dichloride in combination with triethylamine. The reaction involved the dehydrosulfurization of primary thioamides to afford substituted aromatic or aliphatic nitriles in good to excellent yields. The process was also successfully extended to the synthesis of cyanamides starting from the corresponding thioureas and of thiocyanates from dithiocarbamates.
