The reaction of isoprene with aniline, catalyzed by the Pd(acac) 2 3(RO) 3 P3CF 3 CO 2 H system, 1 : 4 : 4 [R = Me, Et; acac = (CH 3 CO) 2 CH], in aniline with a high selectivity (up to 84%) and a nearly quantitative yield (75%). At 1 : 4 : 20 and 1 : 4 : 40 molar component ratios in the catalytic system, up to 28331% of N,N-(2,3-dimethylprop-2-en-1-yl)aniline is formed. Telomeric reaction products appear at 1 : 2 : 4 and 1 : 1 : 10 ratios.Allylamines are used in organic chemistry as basic building blocks for complex organic molecules. The can serve as starting materials in the synthesis of such compounds as a-and b-amino acids, alkaloids, or carbohydrates. One of the most perspective and convenient synthetic approaches to allylamines involves direct amination of 1,3-dienes, catalyzed by complexes of transition metals of the Ni triad. Depending of the nature of the catalytic system, hydroamination of 1,3-dienes is accompanied by their telomerization. Palladium(II) and palladium(0) complexes frequently give 2:1 telomerization products. As shown in [137], the [Pd] : [P] molar ratio of 1 : 4 in the Pd(acac) 2 3 (BuO) 3 P catalytic system is optimal for telomerization of isoprene (I) with various amines in MeCN. With mono-and dialkylamines and with isoprene as 1,3-diene, acid additives in a catalytic system containing palladium(II) diacetylacetonate (acac) complexes and P(III) ligands allow one to control the regioselectivity of telomer formation [133]. With strong acids, such as BF 3 . OEt 2 , N-(3,6-dimethylocta-2,7-dien-1-yl)dialkylamines are formed highly selectively [1]. Evidence for the suggestion that in the presence of noncoordinating acids cationic Pd(II) complexes are formed, that are responsible for the formation of telomers like II, was obtained in [4,5]; therewith, compounds II formed with a selectivity of up to 96%. In the presence of coordinating acids, by varying the composition of catalytic system A [PdX 2 3R 3 P3HX, where HX is acid] one can prepare telomers with a natural 2,6-dimethyloctane skeleton, specifically, a-geranyldialkylamines, with a selectivity of up to 40% [2]. The reactions of isoprene with aromatic amines, unlike those with aliphatic amines, in the presence of catalytic system A provide isoprene hydroamination products (adducts) [638]. Components for catalytic system A were found, that allowed N-(3-methylbut-2-en-1-yl)aniline (III) and methylaniline (IV) to be prepared with a selectivity of 78395% [638], and, therewith, the yield of telomers was no higher than 536%. We studied the reaction of isoprene with aniline, catalyzed by system B [Pd(acac) 2 3(RO) 3 3 CF 3 CO 2 H, where R = Me, Et] in MeCN, aiming at preparing synthetically useful isomeric adducts other than amine III, such as N-(1,2-dimethylprop-2-en-1-yl)aniline (V), N-(1,1-dimethylprop-2-en-1-yl)-aniline (VI), and N-(2-methylbut-2-en-1-yl)aniline (VII), as well as exploring the possibility of formation of telomers VIII3XI (the reactions were performed in sealed glass ampules 25 ml in volume). The resulting data are presente...
