Chlorine dioxide oxidation of amines: synthetic utility and a biomimetic synthesis of elaeocarpidine

Abstract

4829ents,I7 one of them again being Na in liquid NH3.I8 In fact treatment of 6 with this reagent furnishes 4 in 32% yield. 16 Hydrocarbon 4, isolated as a colorless solid (mp 27-30 "C) by preparative GLC on SE 30 at 50 O C , is characterized by its mass spectrum (very similar to that of cubane") [ m / e 104 (15), 103

Heterogeneously Catalyzed Oxidative Cyanation of Tertiary Amines with Sodium Cyanide/Hydrogen Peroxide using Polymer‐Supported Iron(II) Phthalocyanines as Catalyst

“…In the case of secondary amines, this can be achieved either by the use of phenylseleninic acid [7] or via N-chlorination, dehydrochlorination and then trapping of the in-situ generated imine with cyanide. [8] However, tertiary amines can only be converted into a-amino nitriles by the oxidation with wastegenerating oxidants such as chlorine dioxide, [9] mchloroperbenzoic acid, [10] hydrogen peroxide [11] or mercuric acetate, [12] followed by the reaction of the iminium intermediate with cyanide ion. Oxidation with hypervalent iodine compounds, [13] metal-based catalysts such as iron salts, [14] V 2 O 5 [15] have also been reported.…”

Acetone Cyanohydrin: A Convenient Alternative of Toxic Sodium Cyanide/Acetic Acid for Oxidative Cyanation of Tertiary Amines

“…Therefore, the synthesis of these a-aminonitriles is significantly important both in synthetic as well as medicinal chemistry. The classic method known as Strecker reaction [6] involving the one pot condensation of a carbonyl compound, an amine and cyanide in presence of homogeneous [7][8][9] or heterogeneous [10][11][12][13] catalysts is well documented albeit provide poor product yields. Alternatively, the oxidation of tertiary amines with stoichiometric oxidants such as chlorine dioxide [14], m-chloroperbenzoic acid [14,15], hydrogen peroxide [16,17] or mercuric acetate [18], followed by the reaction of the iminium intermediate by cyanide ion represents a simple approach for their synthesis.…”

Biomimetic Synthesis of Ornithine/Arginine and Lysine‐Derived Alkaloids: Selected Examples

“…Glutaraldehyde (51) has been widely used for the synthesis of various heterocycles through the formation of dihydropyridine-type intermediates. The most powerful applications are probably the so-called ''CN(R,S)'' 15) method (Scheme 1.13) with the use of the chiral non-racemic N-cyanomethyloxazolidine ring system integrated in a piperidine structure as an ideal way to stabilize dihydropyridine 58 into compound 59 [prepared in a single step from glutaraldehyde 51, (R)-(−)-phenylglycinol (60) and a source of cyanide ions in water].…”