Palladacycle‐Catalyzed Tandem Allylic Amination/Allylation Protocol for One‐Pot Synthesis of 2‐Allylanilines from Allylic Alcohols

Abstract

An efficient methodology involving the predominant formation of C À C bonds is described for the first direct synthesis of 2-allylanilines from allylic alcohols via a one-pot tandem allylic amination/allylation protocol catalyzed by a palladacycle under mild conditions without the requirement for additional activators.

Anion‐Dependent Imidazolium‐Based Catalysts for Allylation of Aniline with Tunable Regioselectivity

“…The formation of 2‐ and 4‐allylanilines has been less studied. To the best of our knowledge, the formation of 2‐allylanilines ( via allylic substitution of alcohols with anilines) has been achieved using Cu(OTf) 2 , Re 2 O 7 , a palladacycle and iron‐based imidazolium salts (IBLAILs), while the synthesis of 4‐allylanilines has only been reported using Cu(OTf) 2 . A carboxylic acid functionalized graphene oxide and a cubane‐type sulfido cluster incorporating palladium and molybdenum have also been used for the synthesis of 4‐allylanilines, starting from N , N ‐dialkyl substituted anilines, which rules out the possibility of the aniline acting as N‐nucleophile.…”

Lewis‐Acid‐Catalyzed Direct Allylation of Electron‐Poor N‐Heterocyclic Amides through an Amide‐Aldehyde‐Alkene Condensation

“…The reactions catalyzed by Yb(OTf) 3 and Ce(OTf) 3 gave no desired product (entry 5). Similarly, the use of Fe(OTf) 3 , Cu(OTf) 2 or Nd(OTf) 3 gave low yields (entries [6][7][8]. Interestingly, I 2 combined with Fe(OTf) 3 successfully promoted the reaction to deliver a 75 % yield of 4 a (entry 9), while I 2 /Yb(OTf) 3 was not a good catalyst (entry 10).…”

“…The importance of allyl amine derivatives [1] for the synthesis of pharmaceuticals [2] and fine chemicals [3] has attracted considerable interest. In the last decade, most well-established methods for the synthesis of allyl amines and related compounds rely on the transition-metal-catalyzed [4] allylic amination of allyl alcohols [5][6][7][8] and their derivatives. [9][10][11][12] Palladium-catalyzed intraand intermolecular oxidative allylic aminations of non-activated alkenes have been shown an efficient approach to allyl amines in some systems.…”

Intermolecular Insertion of Dialkynylphosphanes into the M–C Bond of Cyclopalladated Rings through Activation by Cyclometallated Amines

“…[4] Recently, we reported that the chiral cyclopalladated naphthylamine complex could be used to catalyse the P-H bond addition reaction to produce a series of enantiomerically pure functionalised mono-and diphosphanes. [6] Electronically, the naphthyl and benzyl complexes are similar. [6] Electronically, the naphthyl and benzyl complexes are similar.…”

“…Recently, we reported that the chiral cyclopalladated naphthyl amine complex could be used to catalyse the P–H bond addition reaction to produce a series of enantiomerically pure functionalised mono‐ and diphosphanes 5. On the other hand, a simple ortho ‐palladated benzyl amine complex was found to be a highly efficient catalyst for the chemoselective C–C bond formation in the synthesis of 2‐allylanilines from allylic alcohols 6. Electronically, the naphthyl and benzyl complexes are similar 7,8.…”