Reductive Heck reactions of N-arylamino-substituted tricyclic imides

Abstract

The CC coupling of (3aR,4S,7R,7aS)-rel-2-[(3-chloro-4-fluorophenyl)amino]-3a,4,7,7a-tetrahydro-4,7-methano-1H-isoindole-1,3(2H)-dione (3) which was prepared as a new starting material and (3aR,4S,7R,7aS)-rel-2-[(2,4-dinitrophenyl)amino]-3a,4,7,7a-tetrahydro-4,7-methano-1H-isoindole-1,3-(2H)-dione (6) with aryl-and heteroaryl iodides gave the aryl(hetaryl), N-arylamino tricyclic imides 4a-d and 7a-d under reductive Heck conditions.

Palladium-Catalyzed Regiocontrollable Reductive Heck Reaction of Unactivated Aliphatic Alkenes

“…On the basis of the preceding results and literature studies on the reductive Heck reaction and palladacycle formation, − ,− we propose a possible catalytic cycle as depicted in Figure . Initially, oxidative addition to aryl triflate is conducted by in situ generated active (Cy-JohnPhos) 2 Pd 0 catalyst.…”

“…The intermolecular reactions have been primarily limited to cyclic olefins. For example, specific bi - and oligocyclic alkenes like norbornenes are ideal substrates . The rigidity of the carbocyclic framework in these substrates does not allow the alkyl palladium intermediate to undergo rotation to form the usual Heck product, thus the intermediate reacts with the hydride donor instead.…”

“…The choice of suitable hydride source was also critical. Since the combination of amine/acid has been reported to act as an effective reductant in Pd-catalyzed reactions, ,, several combinations of amine (Et 3 N, i Pr 2 NEt and etc.) and TFA were examined (Table S4).…”