Pd×Et₃B‐Catalyzed Alkylation of Amines with Allylic Alcohols.

Abstract

Amines Amines Q 0120Pd·Et 3 B-Catalyzed Alkylation of Amines with Allylic Alcohols. -A combination of catalytic amounts of palladium and Et 3 B promotes allylic alkylation of primary and secondary aromatic and aliphatic amines by the direct use of allylic alcohols, providing tertiary amines in high yields. -(KIMURA*, M.; FUTAMATA, M.; SHIBATA, K.; TAMARU*, Y.; Chem. Commun. (Cambridge) 2003, 2, 234-235; Dep. Appl. Chem., Fac. Eng., Nagasaki Univ., Bunkyo, Nagasaki 852, Japan; Eng.) -M. Paetzel 18-072

Transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates

“…The enamine (generated in situ) attacks the p-allypalladium complex 21, giving complex 22 via TS [21][22] . 40 (E)-Isomers were formed preferentially in good yields with addition to the least substituted end of the allylic terminus ( Table 8). 31 2.1.3.…”

Triethylborane (Et3B)

“…10 Triethylborane can also be used as a radical initiator in both ionic liquids 11 and in aqueous systems. 8,12 Triethylborane has also found application in non-radical processes, such as promoting the palladium-catalysed allylation of active methylene compounds 13 and amines 14 with unactivated allylic alcohols and the triethylboranetriggered intermolecular domino three-component Michael-aldol reaction. 15 It has been noted, especially for radical reactions, that the quality of the triethylborane used is critical.…”

Procedures for and Possible Mechanisms of Pd‐Catalyzed Allylations of Primary and Secondary Amines with Allylic Alcohols

“…as an additive with either Pd(PPh 3 ) 4 or Pd-(OAc) 2 /P(n-Bu) 3 as the catalyst. [59] The optimum catalyst, amount of BEt 3 , reaction temperature, and reaction time depend on the natures of both alcohol and amine [Equations (27) and (28)]. [60] The results obtained from isomeric allylic alcohols depicted in Equation (29) www.eurjoc.orgpalladium.…”