Regio- and enantioselective copper-catalyzed addition of dialkylzinc reagents to cyclic 2-alkenyl aziridines

Asymmetric Ring‐Opening of Epoxides and Aziridines with Carbon Nucleophiles

“…On the other hand, Pineschi et al have shown that this RKR process is not operative with cyclic allylic aziridines: with these substrates it is only possible to obtain a classic kinetic resolution that gives new allylic amines with moderate to good enantioselectivity 72…”

Identification of a Valuable Kinetic Process in Copper‐Catalyzed Asymmetric Allylic Alkylation

“…[3] In 1998, Pineschi, Feringa, and co-workers achieved pioneering work in this field with the kinetic resolution of cycloalkadiene monoepoxide in the presence of chiral phosphoramidite ligands. [4] A few years later, the same groups established that the enantiomers of the racemic allylic epoxide might have different reactivity under the reaction conditions and that they could be selectively transformed into two distinct regioisomers (regiodivergent kinetic resolution). [5] Recently, our group reported on the development of a dynamic kinetic asymmetric transformation (DYKAT).…”

Aliphatic Nucleophilic Substitutions: Problematic Electrophiles

“…Organocopper reagents, being soft nucleophiles, often lead to Sn2¢ reactions when treated with allylic [227][228][229] or propargylic [230][231][232] electrophiles. Although highly stereoselective reactions with clean attack from the opposite side of the leaving group can be achieved [233] (Scheme 4.56), these reactions might still require careful optimization of the conditions to achieve high-yielding, stereoselective product formation, because the precise structure of the organocopper reagent and the solvent can have a decisive impact on the selectivity (Scheme 4.56).…”