Direct asymmetric N‐specific reaction of nitrosobenzene with aldehydes catalyzed by a chiral primary amine‐based organocatalyst

Abstract

Nitroso compounds have two reactive nitrogen and oxygen atoms. It is interesting and important to perform a nitrogen or oxygen selective reaction with interesting substrates. These atom specific reactions are crucial to specifically synthesis of specific compounds. An enantioselective N-specific reaction of nitrosobenzene with unmodified aldehydes was successfully achieved catalyzed first by a variety of primary amine-based organocatalysts with higher yield and enantioselectivity. The bulkier substituted groups of the organocatalyst and two hydrogen bonds from the organocatalyst and the oxygen atom of nitrosobenzene make the reaction preferentially N-specific and predominantly afford R products.

Enhanced Sensing of 4-Nitroso-N,N–Dimethyl Aniline using Multi-Walled Carbon Nano Tube Modified Glassy Carbon Electrode

“…For example, in dimerization, they play an ambivalent role: a molecule of nitroso compound behaves as the nucleophile, whereas in another molecule, the nitrogen atom of the nitroso group plays the role of an acceptor [9]. These compounds were also used in the synthesis of some natural product building blocks with high enantiomeric purity [10]. On the other hand, the presence of two heteroatoms (oxygen and nitrogen) in the nitroso group makes these compounds suitable as ligands for the synthesis of a wide variety of metal complexes [11].…”

Electrochemical Study of 4-Nitroso-N,N-dimethylaniline in Nonaqueous Solvents

“…1 These compounds were also used in the synthesis of some natural product building blocks with high enantiomeric purity. [2][3][4][5] On the other hand, the presence of two heteroatoms (oxygen and nitrogen) in the nitroso group makes these compounds suitable as ligands for the synthesis of a wide variety of metal complexes. [6][7][8][9][10] From the medical point of view, nitroso compounds are also important.…”

Direct Asymmetric α Benzoyloxylation of Cyclic Ketones

“…Nevertheless, while numerous secondary amine catalysts have been employed in the a oxygenation of aldehydes and ketones, [2] the use of primary amines in this transformation has been virtually non-existent. [9] This is surprising in light of the growing use of primary amine catalysts for the functionalization of diverse substrate classes, including ketones, enones, a-branched enals, and aldehydes. [10] On the basis of these considerations, we envisioned that the readily available primary amines of type 9, derived in a single step from cinchona alkaloids, could catalyze a direct enantioselective a oxygenation of ketones.…”