Palladium(II)-Catalyzed Intramolecular Diamination of Unfunctionalized Alkenes

Abstract

Intramolecular diamination reactions are described which yield cyclic ureas as direct products of an oxidative alkene transformation in the presence of palladium acetate and iodosobenzene diacetate as terminal oxidant. The reaction is truly catalytic in metal catalyst and represents the proof of principle for this elusive type of alkene oxidation.

Copper‐Catalyzed Cyclization and Azidation of γ,δ‐Unsaturated Ketone O‐Benzoyl Oximes

“…[1] As a result, significant progress has been made recently in this aspect with the development of new transition metalcatalyzed proc 2] When the olefin diamination is realized in an intramolecular manner by tethering one (or two) nitrogen atom(s) with the alkene moiety, functionalized nitrogen heterocycles will be furnished. As such, several important methodologies employing palladium, [3] nickel, [4] gold, [5] and copper [6] as catalyst have been developed for this purpose. However, these studies mainly deal with unsaturated amide or sulfonamide derivatives, whereas reactions involving other types of nitrogen sources have much less been explored.…”

“…Abstract: An intramolecular imination/azidation sequence has been realized through the tetrak-A C H T U N G T R E N N U N G is(acetonitrile)copper(I) hexafluorophophate [Cu(CH 3 CN) 4 PF 6 ]-catalyzed reaction of g,d-unsaturated ketone O-benzoyl oximes with trimethylsilyl azide (TMSN 3 ). The reaction proceeds via the copper-mediated N À O cleavage and subsequent C À N forming 5-exo cyclization.…”

Palladium-Catalysed Intermolecular 1,2-Diamination of Alkenes

“…[1][2][3] Within this context, the application of suitable high oxidation state palladium catalysis 4 represents a key methodology.…”

Pyrrolidine and Piperidine Formation via Copper(II) Carboxylate Promoted Intramolecular Carboamination of Unactivated Olefins: Diastereoselectivity and Mechanism.

“…Methods that provide for concise build-up of functionality by installing two rings in a single operation may prove especially useful in the concise synthesis of nitrogen heterocycles for natural product synthesis and drug discovery endeavors. 11,14,15,[26][27][28][29][30][31][32] Herein is reported an expansion of the substrate scope of the copper(II) promoted intramolecular carboamination of unactivated alkenes, 11 a transformation that installs two new rings from acyclic N-substituted amines.…”