Intramolecular Palladium‐Catalyzed Aminocarboxylation of Olefins as a Direct Route to Bicyclic Oxazolidinones

Abstract

An efficient, direct synthesis of oxazolidinones fused to six-membered heterocyclic rings starting from carbamate-protected aminoalkenes has been developed. This procedure is based on an oxidative palladium(II)-catalyzed reaction performed in the presence of stoichiometric copper chloride, which is determinant to promote the formation of the bicyclic product and prevent the isolation of the monocyclic amination product. Oxazolidinone compounds arise from a domino aminocarboxylation process through the direct intervention of the carbamate oxygen after the initial palladium-promoted transfer of the nitrogen atom on the C=C double bond.

Intra‐Intermolecular Palladium‐Catalyzed Domino Reactions of Glycine Allylamides for the Synthesis of Diversely Functionalized Piperazinones

“…[b] The reactions were carried out at room temperature (Entries 1-12), at reflux (Entries [13][14][15], and at 100°C (Entries [16][17][18].…”

“…More specifically, N-Boc-glycine allylamides (Boc = tert-butoxycarbonyl, Figure 1, path a) [15] and alkenylureas ( Figure 1, path b) [16] were converted by aminooxygenation and diamination processes into oxazole-and imidazole-fused piperazinones, respectively. Herein, we describe the intraintermolecular conversion of glycine allylamides into piperazinones that contain functional groups for further conversion into more complex structures.…”

Mild and High‐Yielding Molybdenum(VI) Dichloride Dioxide‐Catalyzed Formation of Mono‐, Di‐, Tri‐, and Tetracarbamates from Alcohols and Aromatic or Aliphatic Isocyanates

“…Both catalysts are cheap, odorless, non-toxic, and non-volatile solids. In a typical experiment 100 ppm of MoO 2 Cl 2 A C H T U N G T R E N N U N G (DMF) 2 sufficed at room temperatuere for catalyzing the addition of (À)-menthol (10) to N-phenyl isocyanate (2). This reaction furnished carbamate 11 in 100% yield after just 20 min.…”

“…In crop protection carbamates serve as insecticides. [7] Carbamates are not only synthetic targets [8] but are also used as O-nucleophiles, [9] N-nucleophiles, [10] protective groups [11] and radical progenitors.…”

Access to pyrrolo-pyridines by gold-catalyzed hydroarylation of pyrroles tethered to terminal alkynes

“…During our studies aimed at the synthesis of complex heterocyclic systems by intramolecular transition-metal-catalyzed protocols [20–32], we reported an arylative Pd-catalyzed cyclization of N -allyl-pyrrole-2-carboxamides, affording pyrrolo[1,2- a ]pyrazines or pyrrolo[2,3- c ]pyridines (Scheme 1) [33]. The reaction provided also the isomeric pyrrolo[3,2- c ]pyridines arising from 1,2-migration of the amide moiety.…”