Pd-Catalyzed Three-Component Reaction of Anilines, Ethyl Vinyl Ether, and Nitro-Paraffin: Assembly of β-Nitroamines

Abstract

A novel palladium-catalyzed amination and nitration of ethyl vinyl ether for the construction of β-nitroamine derivatives under mild conditions has been developed. This transformation provides a new strategy for the installation of amino and nitro from aromatic amines and nitro-paraffin into alkenes. Morpholine resulted in the aza-Henry reaction, while DABCO led to the unexpected rearrangement.

Alkyl Enol Ethers: Development in Intermolecular Organic Transformation

“…Jiang and co‐workers introduced a Pd‐catalyzed synthesis of β‐nitroamines from acyclic enol ether, aniline 72 and nitroalkane [43] . In this method, first an imine intermediate has been formed in the existence of Pd‐catalyst via interaction of aniline 72 and ethyl enol ether, followed by the elimination of ethanol.…”

Recent Advances in Transformations Involving Electron‐Rich Alkenes: Functionalization, Cyclization, and Cross‐Metathesis Reactions

“…Later, the same group developed an elegant Pd‐catalyzed amination and nitration of ethyl vinyl ether for the synthesis of structurally important β ‐nitroamine derivatives (Scheme 10). [24] Different from the classic aza ‐Henry reaction started with imines, this method provides a novel strategy utilizing amines and ethyl vinyl ether as readily available materials in situ generating imine intermediates to form β ‐nitroamines 10‐3 under mild conditions. Several mechanistic experiments of time course were conducted, and the results suggested that 10‐3 could be converted to the β ‐methyl‐ β ‐nitroamine products 10‐4 under this catalytic system.…”