Synthesis of trans-2,5-dimethylpyrrolidine by intramolecular amidomercuration

Abstract

As part of another synthetic project, we became interested in the stereoselectivity of the electrophile-initiated cyclization of -alkenyl amine derivatives (1 -*• 2). In the NH G

Evolution of copper(II) as a new alkene amination promoter and catalyst

“…By surveying a number of literature reports and observing results of additional reactions conducted in our own lab [10], we found that for intramolecular alkene aminations of secondary amines, the nitrogen radical [25–27] and the trans-amino-metallation mechanisms [28,29] generally favor formation of 2,5-trans pyrrolidines while cis-aminometallation mechanisms [22,30–32] favor formation of 2,5-cis pyrrolidines.…”

Mono-cyclopentadienyl complexes of lanthanum: synthesis and characterization of anilido derivatives

“…Pyridine was purchased from Aldrich and distilled over sodium benzophenone prior to use. [g 5 -C 5 H 2 (SiMe 3 ) 3 -1,2,4]K [40,41], LaI 3 (THF) 4 [21], KNHAr [42], (Cp 000 )LaI 2 (py) 3 (1) [19], (Cp 000 )LaI 2 (bipy)(py) (5) [19] and 2-amino-hex-5-ene (7) [43,44] were prepared according to literature procedures. Hexanes, toluene, tetrahydrofuran and diethyl ether were de-oxygenated by passage through a column of supported copper redox catalyst (Cu-0226 S) and dried by passing through a second column of activated alumina [45].…”

Evidence for Alkene cis‐Aminocupration, an Aminooxygenation Case Study: Kinetics, EPR Spectroscopy, and DFT Calculations

“…Initial mechanism proposal : A comparison18 of the high 2,5‐ cis ‐pyrrolidine stereoselectivity in the copper(II) carboxylate promoted, alkene aminooxygenation24 of α‐substituted‐γ‐alkenylsulfonamides [Eq. (1), vide supra] with analogous intramolecular alkene amination reactions that proceed via trans ‐aminometallation18, 31, 32 (outer sphere) and cis ‐aminometallation18, 33–36 (inner sphere) mechanisms led us to postulate that, stereochemically, the copper‐promoted reaction is more similar to reactions that proceed through cis ‐aminometallation mechanisms than to those that proceed through trans ‐aminometallations. We proposed that the resulting organocopper(II) intermediate underwent CCu homolysis29, 37–39 to generate the carbon radical, and direct trapping of the radical with TEMPO40, 41 provided the observed aminooxygenation product (Scheme ).…”