Palladium-catalyzed highly regioselective and stereoselective arylation of electron-rich allylamines with aryl bromides

Cross‐Coupling Arylations: Precedents and Rapid HistoricalReview of the Field

“…Pd(OAc) 2 was the catalyst used in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or hydroquinone (HQ) as the additive, leading exclusively to γ-arylated (E)-allylamines in good to excellent yields [58] ( Figure 1.9). Ligand 7a was the most successful ligand used and, in all cases, the R-enantiomer of the kinetic product (8 or 10) was preferred.…”

“…Heck-Mizoroki reactions on other N-protected allylamines with aryl bromides by Xiao and coworkers[58]. 10 Heck-Mizoroki reactions on N-Boc protected allylamines with aryl bromides by Xiao and coworkers[58].…”

“…Scheme 1 58. Large-scale Negishi-Baba coupling in the synthesis of PDE472 by Novartis Pharma AG[37].…”

Substrate-Directed Heck–Matsuda Arylations

“…2 Aiming at this important goal, we have been investigating the Pd-catalyzed arylation of olefins with arenediazonium salts, known as Heck-Matsuda reaction. 5 Arenediazonium salts are considered by some researchers as hazardous materials due to their high reactivity 6 and the low thermostability of some members of this family of compounds. 3 Indeed, the high levels of chemo-and stereocontrol observed in these reactions usually do not depend on the use of halide scavengers (such Ag + or Tl + salts), dry solvents, inert atmosphere, or phosphane ligands (Scheme 1).…”

Palladium‐Catalyzed Highly Regioselective Mizoroki–Heck Arylation of Allylamines with Aryl Chlorides

“…During our investigation of the regioselective arylation of allylamines,18 we reported that the highly regioselective internal Mizoroki–Heck arylation of N ‐Boc‐allylamine (Boc= tert ‐butyloxycarbonyl) with aryl bromides could proceed smoothly with palladium–dppp (dppp=1,3‐bis(diphenylphosphino)propane) catalysts in ethylene glycol (EG) and Pd(OAc) 2 could catalyze the coupling reaction of aryl bromides with bulky N , N ‐diprotected allylamines under ligand‐free conditions in water or DMF, preferentially giving the γ‐arylated products 18a,b. More recently, we found that the highly regioselective direct arylation of allylamines with thiophenes and furans could be accomplished with Pd(OAc) 2 and suitable additives 18c.…”