Direct palladium/carboxylic acid-catalyzed allylation of anilines with allylic alcohols in water

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

“…[1,2] However, due to the inertness of the hydroxy moiety in such scenarios, direct substitutions of allylic alcohols typically require high temperatures, [3] neat conditions, [4] or considerable amounts of activators. [5][6][7][8][9][10][11][12][13][14] To date, there are several reports on the transition metal-catalyzed allylic amination of allylic alcohols or allylic alcohol derivatives with arylamines leading to the predominant generation of N-allylanilines via C À N bond formation.…”

“…The electronic character of the arylamines seems to greatly influence the regioselectivity, while the reactivity towards allylic amination seems relatively unaffected. As shown in Table 2 , electron-donating groups at the para position of anilines enhanced both reactivity and selectivity in favour of the C-allylated products ( Table 2, entries 1-3), while the presence of a electron-withdrawing group such as nitro or carboxylate favoured the N-allylated products ( Table 2, entries [12][13][14] and no C-allylated product was observed in such instances. This trend however seems to be disrupted when a very strong electron-withdrawing group like trifluoromethyl (Table 2, entry 6) is involved.…”

Platinum-Catalyzed Direct Amination of Allylic Alcohols

“…5 In terms of atom economy 10 and environmental impact, the development of a direct catalytic substitution of underivatized allylic alcohols 1 with amines 3, which produces the desired allylamines 4 together with water as the sole coproduct (1 6 4), is more straightforward and desirable. 6 However, for overcoming the poor leaving ability of the hydroxyl group, the previously reported catalytic direct aminations require rather severe reaction conditions and/or the addition of considerable amounts of an activator such as 20 including an ef cient enantioselective variant. 21 In 2002, Ozawa and Yoshifuji reported that several palladium complexes supported by sp 2 hybridized phosphorus ligands catalyzed direct aminations of allylic alcohols 1 without the use of an activator.…”

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

“…[61] Yang's team, who had previously used the PdL n /Ti-(OR) 4 /MS procedure in benzene for allylation of anilines, [40,[48][49][50][51]55] has recently reported the use of a carboxylic acid as the additive at reflux in water [Equations (31)- (33)]. [62] A screening of carboxylic acids and palladium/ligand combinations resulted in the retention of adamantane-1-carboxylic acid (AdCO 2 H) and Pd(acac) 2 /PPh 3 for the performance of various allylic aminations. No more than a 10 % yield of allylation product was obtained from aniline and cinnamyl alcohol in the absence of the carboxylic acid.…”