23784-49-8

Usage

InChI:InChI=1/C13H17NO/c1-11(2)10-14-13(15)9-8-12-6-4-3-5-7-12/h3-9,11H,10H2,1-2H3,(H,14,15)

Upstream product

• 126437-19-2 1-cinnamoyl-2,2-dimethylaziridine 
• 112753-90-9 N-cinnamoyl-2,2-dimethylaziridine 
• 201230-82-2 carbon monoxide 
• 78-81-9 isobutylamine 
• 536-74-3 phenylacetylene 

Relevant academic research and scientific papers

Enhancing Ligand-Free Fe-Catalyzed Aminocarbonylation of Alkynes by ZrF4

Zirconium fluoride was utilized to promote efficiently iron-catalyzed aminocarbonylation between alkynes and amines without the use of extra ligands. In particular, this new system is applicable to a wide range of amine and alkyne substrates affording α,β-unsaturated amides in good to excellent yields. Preliminary mechanistic studies reveal the activation model involving interactions of ZF4 with both iron catalyst and amine substrates.

Three positional isomers of substituted triphenylmethanes from reactions of trityl anion with 1-acyl-2,2-dimethylaziridines

Ring opening of aziridines 4a-d in reactions with trityl anion Tr(-) proceeds exclusively by cleavage of the NCMe2 bond.Substitution of the benzylic carbon of Tr(-) leads to 'central' products 10a-d in yields of 0-5percent.This is ascribed to an SN2 reaction with borderline character, as is well known from reactions of aziridines 4a-d with other nucleophiles.All remaining ring-opening reactions result from single-electron transfer (SET).This is direct SET from Tr(-) to aziridines 4a-c.For compound 4d (acyl = cinnamoyl), the SET reaction is of the innersphere type and proceeds via Michael addition, at least in part.Homolytic ring opening of the generated aziridino ketyls 5 forms the tertiary amidatoalkyl radicals 6.Main reaction of radicals 6a-c is transfer of a hydrogen atom from one of its two methyl groups to the generated trityl radical Tr..Methallylamides 7 and enamides 8 are the final products. ortho-Substituted triphenylmethanes 12 and/or its olefinic precursors 13 arise in ca. 20percent yield.A mechanism for the formation of these unique products is proposed that first converts the radicals 6 into the corresponding carbanions 16 which undergo an SN2' reaction with one allylic system TrCHCH=CH* of the dimer 14 of Tr..The leaving group Tr(-) is eliminated from this partial structure when carbanions 16 attack the marked carbon converting it finally into the substituted ortho carbon of compounds 12.Addition of radicals 6 to Tr(-) is probably the way to the para-substituted triphenylmethanes 11, which arise in yields of only 0-1percent from aziridines 4a,b (acyl = benzoyl, pivaloyl).Higher yields of para-substituted compounds 11 are obtained from aziridines 4c (acyl = 4-phenylbenzoyl) and 4d.This is ascribed, at least for substrate 4c, to a chain reaction because ketyl 5c must be formed more rapidly than ketyls 5a,b.A substantial part of radical 6d cyclizes, ending up as the triphenylmethane compound 26 that carries a pyrrolidone ring in the para position.

Evolutions differentes de radicaux anions formes par voie chimique ou electrochimique

Chemical and electrochemical reductions of N-aroylaziridines 1 are described and compared.The first step is a single electron transfer (1 +e -> 1-. -> 1'-.).But compounds obtained from 1'-. are depending on the method used way followed: chemical reduction of N-cinnamoylaziridine 1e provides pyrrolidone 10e; but oxazoline 11e is available by electrochemical reduction of the same starting material 1e.Counter ion seems responsible of these different results.In agreement with this hypothesis, it is shown that pyrrolidone 10e is obtained from 1j only in presence of a counter ion.

REDUCTIVE RING OPENING OF N-ACYLAZIRIDINES: DIFFERENT OUTCOMES OF CHEMICAL AND ELECTROCHEMICAL REACTIONS

Main products from electrochemical reduction of two N-acylaziridines are the corresponding oxazolines which are not formed in chemical reduction, probably due to a coordination of the oxygen with a metal counter-ion.