Silver(I)-catalyzed oxidation of cyclic secondary amines with peroxodisulphate

Abstract

Oxidation of piperidines, pyrrolidine, azetidine, perhydroazepine, and perhydroazocine with aqueous alkaline sodium peroxodisulphate in the presence of silver nitrate gave 1,l '-bipiperidines, a trimer of 1pyrroline, 1,l '-biazetidine, 1,l'biperhydroazepine together with 1 -formylperhydroazepine, and 1 -formylperhydroazocine, respectively.An electron-transfer process in the silver(1)-catalyzed oxidation with peroxodisulphate has recently been recogni~ed.~-~ In the presence of silver(1) ion, peroxodisulphate decomposes according to equations ( 1) and ( 2):

Synthesis of tryptamines by the Fischer method using synthetic precursors and latent forms of amino-butanal (review)

“…Early methods for the synthesis of the trimer 3 involved the reaction of pyrrolidine and tetramethylenediamine with hypochlorites by a modification of the procedure in [164] and also hydrolysis by a methanol solution of 1-formyl-2-methoxypyrrolidine hydrochloride (44% a of 3 together with 16% a of aminobutanal dimethyl acetal) [165]. A method with oxidation of pyrrolidine in an aqueous alkaline medium with sodium persulfate has preparative significance [159,166].…”

Computational Exploration of the Photocycloaddition of Imines to Alkenes

“…For isoxazoline derivatives 3 and 4, the active space included 10 electrons in 9 orbitals (4 p, 4 p* and n orbital for nitrogen). In all cases, two more electrons and orbitals were included for the reaction with ethylene, which in the larger case gave an active space of (12,11). The zeroth order wavefunction used in the single-point CASPT2 calculations needed for the re-evaluation of the energy profile is a three root (S0, S1, S2) state average CASSCF wavefunction.…”

“…The structure of the conical intersection (CI) funnels associated with each path were optimized by applying the methodology included in GAUSSIAN 03. [10] Pyrroline (1) is not experimentally accessible, [11] but it represents a useful first contact to evaluate the effect of structural constraint. The tentative active space includes the nitrogen atom n orbital and the p and s bonding and anti-bonding orbitals for the CÀN bond.…”

Ammonium Peroxydisulfate

“…63 Secondary amines yield a variety of products, generally in poor yield, 60,64 but piperidines give good yields (40-60%) of 1,1-bipiperidines. 65 CHO (13) Transformation of Carboxylic Acids to Peroxy Acids and Decarboxylation. Carboxylic acids are converted (80-90% yield) to the corresponding peroxy acids at room temperature under phase-transfer conditions.…”