Oxidative Deamination of α-Aminophosphonates and Amines by Zinc Dichromate Trihydrate (ZnCr2O7˙3H2O) under Solvent-Free Conditions at Room Temperature

Abstract

O x i d a t i v e D e a m i n a t i o n o f a -A m i n o p h o s p h o n a t e s a n d A m i n e s

Metal-free hypervalent iodine/TEMPO mediated oxidation of amines and mechanistic insight into the reaction pathways

“…This selectivity is in contrast with other oxidizing agents used in earlier reports. [3][4][5][6][7][8][9][10][11] Isobutyl-methylamine also well reacted under identical conditions to provide corresponding isobutyraldehyde 2o in excellent yield of 89% (Scheme 3). Oxidation of symmetrical amines such as dibenzylamine using PhI(OAc) 2 (1 equiv) and TEMPO (0.1 equiv) in dry CH 2 Cl 2 provided the mixture of benzaldehyde (2b) and benzyl amine (1b) in 1 : 1 ratio in the good yield of 90% yield.…”

“…The oxidation of amines is also used as a powerful tool to produce different synthetic intermediates: imines, nitriles, oximes and amides. 2 In the last two decades, several protocols reported the synthesis of carbonyl compounds from amines using metal reagents/catalysts such as KMnO 4 , 3 ZnCr 2 O 7 , 4 nicotinium dichromate, 5 palladium, 6 copper 7 and ruthenium. 8 These traditional methods suffer from their own limitations, such as use of stoichiometric amounts of reagents/catalysts, inherent toxicity of metals, high temperature and limited substrate scope.…”

Reductive Deamination by Benzyne for Deoxy Sugar Synthesis Through a Domino Reaction

“…Deamination, the removal of an amine group from a molecule, plays an important role in chemical transformations and biological systems . Chemical reagents developed for this purpose include copper(II) halides along with alkyl nitrites; HCO 2 H/acetic anhydride (Ac 2 O) followed by POCl 3 /Et 3 N and then tributyltin hydride; hydrogen peroxide along with tetrabutylammonium iodide as the catalyst; isopropyl N , N ‐difluorocarbamate; nitrosyl acetate; nitrosyl tetrafluoroborate; p ‐nitrophenyl formate, Ac 2 O, POCl 3 /Et 3 N, and tributyltin hydride in sequence; samarium iodide; sodium borohydride along with 2,3,5,6‐tetraphenylpyrylium tetrafluoroborate; sodium nitrite; and zinc dichromate trihydrate . Deamination of amino acids and proteins can proceed through an oxidative process by using molecular oxygen in the presence of a d ‐amino acid oxidase, lysine cyclodeaminase, l ‐lysine oxidase, pyridoxal phosphate cofactor, and so forth.…”

A Mechanochemical‐Assisted Oxidation of Amines to Carbonyl Compounds and Nitriles

“…The conventional route to aldehydes and ketones involves the oxidation of primary and secondary alcohols, but a challenging alternative is the synthesis of carbonyl compounds from readily available and abundant precursors like amines. The existing methodologies, despite their efficiency, suffer from the required use of stoichiometric amounts of toxic metal‐containing reagents, such as KMnO 4 , argentic picolinate, ZnCr 2 O 7 trihydrate, and nicotinium dichromate, or palladium‐, copper‐, and ruthenium‐based catalysts, and toxic solvents.…”