Synthesis of Primary Allylic Amines

Efficient synthesis of allylamines from a novel (E)-2,3-difunctionalized allyl bromide

“…It should be noted that the synthesis of allyl bromide 4 was always accompanied by the formation of its regioisomer 5, which was easily separable from the desired product 4 by silica gel column chromatography (Scheme 3). In order to establish a chemical library reserved for the various functionalized allylamines published during the last decade by our research group 30 and their use as basic skeletons of many biologically important substances [31][32][33][34][35][36][37] and numerous natural products [38][39][40][41][42][43][44][45][46][47] , we focused our attention on the synthesis of a new family of allylamines 6. The best reaction conditions were obtained following the reaction of the electrophilic allyl bromide (E)-4 with excess of monoalkylamines (2 equiv.)…”

Platinum-Catalyzed Direct Amination of Allylic Alcohols

“…Takashi Ohshima 1 and Kazushi Mashima derivatives 2 with nitrogen nucleophiles 3 is well established to proceed through, the rst oxidative addition of allylic substrates to a low valence metal center, forming π allylmetal intermediates 6, followed by nucleophilic addition of amines gives allylamines due to the new carbon nitrogen bond formation with high regio , stereo , and enantioselectivity. 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.…”

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

“…Furthermore, allylamines are valuable synthetic intermediates [10] for the preparation of numerous compounds, such as amino acids, [11] piperidines, [12] and azacarbohydrates, [13] and also for reactions involving ringclosing alkene metathesis methodology. [14] Since the acceptance of our reviews, [15] the synthesis of allylic amines from allylic alcohols via η 3 -allylpalladium intermediates has been the subject of new reports and it seems of interest to highlight this topic in commenting on the reaction mechanisms.…”

“…Although usually carried out in the presence of Na 2 CO 3 [Equations (12)- (14)], the process also takes place under neutral conditions [Equations (10) and (11)], thus excluding the formation of transient allyl hydrogenocarbonate from 1 and CO 2 liberated from Na 2 CO 3 . The involvement of allyl acetate through transesterification with EtOAc was excluded from the successful reaction, in H 2 O/Et 2 O, between allyl alcohol and a C-nucleophile.…”