Synthesis of Pyrrolidines and Pyrroles by Tandem Amination/Cyanation/Alkylation and Amination/Oxidation Sequences

Abstract

Starting from a primary amine-tethered alkyne 1, a copper-catalyzed three-component tandem amination/cyanation/alkylation sequence gives α-CN pyrrolidine 6 in good yield and regioselectivity. Also, a silver mediated tandem amination/oxidation of a secondary amine-tethered alkyne 7 produces functionalized pyrrole 8 in good yield. All reactions were conducted in one pot without any protection/deprotection steps.

Late Transition Metal-Catalyzed Hydroamination and Hydroamidation

“…This intramolecular hydroamination/nucleophilic addition cascade was extended to various nucleophiles such as TMSCN, TMSCF 3 , and phosphinates to give α-CN-, α-CF 3 -, and α-PO­(OR) 2 -substituted N -heterocycles with ring sizes of 5–7 (Scheme ). − …”

Production of Quaternary α-Aminonitriles by Means of Indium-Catalyzed Three-Component Reaction of Alkynes, Amines, and Trimethylsilyl Cyanide

“…Thus, we next attempted to apply this protocol to intramolecular hydroamination. Recently, Hammond et al reported the one-pot synthesis of α-CN N-heterocycles from alkynylamines with Me 3 SiCN using a copper­(I) or a gold­(I) catalyst under microwave conditions . It was assumed that the reaction would proceed via the intramolecular hydroamination of alkynylamines, followed by the addition of Me 3 SiCN to form α-cyanated heterocycles.…”