Pyrrolidine and piperidine formation via copper(II) carboxylate-promoted intramolecular carboamination of unactivated olefins: diastereoselectivity and mechanism.
An expanded substrate scope and in-depth analysis of the reaction mechanism of the copper(II) carboxylate-promoted intramolecular carboamination of unactivated alkenes is described. This method provides access to N-functionalized pyrrolidines and piperidines. Both aromatic and aliphatic gamma- and delta-alkenyl N-arylsulfonamides undergo the oxidative cyclization reaction efficiently. N-Benzoyl-2-allylaniline also underwent the oxidative cyclization. The terminal olefin substrates examined were more reactive than those with internal olefins, and the latter terminated in elimination rather than carbon-carbon bond formation. The efficiency of the reaction was enhanced by the use of more organic soluble copper(II) carboxylate salts, copper(II) neodecanoate in particular. The reaction times were reduced by the use of microwave heating. High levels of diastereoselectivity were observed in the synthesis of 2,5-disubstituted pyrrolidines, wherein the cis substitution pattern predominates. The mechanism of the reaction is discussed in the context of the observed reactivity and in comparison to analogous reactions promoted by other reagents and conditions. Our evidence supports a mechanism wherein the N-C bond is formed via intramolecular syn aminocupration and the C-C bond is formed via intramolecular addition of a primary carbon radical to an aromatic ring.
Sherman
Eric S
ES
Department of Chemistry, The University at Buffalo, The State University of New York, Buffalo, New York 14260, USA.
Fuller
Peter H
PH
Kasi
Dhanalakshmi
D
Chemler
Sherry R
SR
D000475:Alkenes / Q000737:chemistry*; D000586:Amination; D002264:Carboxylic Acids / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003500:Cyclization; D005609:Free Radicals / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry; D010084:Oxidation-Reduction; D010880:Piperidines / Q000138:chemical synthesis* / Q000737:chemistry; D011759:Pyrrolidines / Q000138:chemical synthesis* / Q000737:chemistry; D012997:Solvents; D013237:Stereoisomerism; D013449:Sulfonamides / Q000737:chemistry; D013696:Temperature; D014867:Water / Q000737:chemistry
D000475:Alkenes; D002264:Carboxylic Acids; D005609:Free Radicals; D010880:Piperidines; D011759:Pyrrolidines; D012997:Solvents; D013449:Sulfonamides; D014867:Water; C032727:piperidine; D003300:Copper; C032519:pyrrolidine; D009584:Nitrogen