A strategy for the palladium-catalyzed dehydrative tandem benzylation of 2-morpholinoanilines with benzyl alcohols has been developed. This cascade reaction is devised as a straightforward and efficient synthetic route for N-(1,2-diphenylethyl)-2-morpholinoanilines in moderate to good yields (50–81%). The dehydrative sp³ C–H bond benzylation proceeds chemoselectively at the benzylic position of N-benzyl-2-morpholinoaniline to form a new C(sp³)–C (sp³) bond. KIE experiments show that C–H bond activation is involved in the rate-determining step (KIE = 2.7). A Hammett study of 2-morpholinoanilines gives a negative ρ value, suggesting that there is a build-up of positive charge in the transition state. A “on water” protocol, which affords the corresponding desired products with water as the sole co-product, can be achieved under mild reaction conditions without the need for bases or other additives in an atom-economical process.

中文翻译：

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钯催化的2-吗啉代苯胺在水上的脱水N-苄基化/ CH苄基化级联反应

已经开发了用苯甲醇钯催化2-吗啉代苯胺的脱水串联苄基化的策略。该级联反应被设计为N-（1,2-二苯乙基）-2-吗啉代苯胺的简单有效的合成途径，产率中等至良好（50-81％）。脱水的sp ³ C–H键苄基化反应在N-苄基-2-吗啉代苯胺的苄基位置发生化学选择性，形成一个新的C（sp ³）–C（sp ³）键。KIE实验表明，CH键的活化参与了速率确定步骤（KIE = 2.7）。Hammett对2-吗啉代苯胺的研究得出负ρ值，表明在过渡态中存在正电荷的积累。可以在温和的反应条件下实现“水上”方案，该方案以水作为唯一的副产物提供相应的所需产品，而无需在原子经济过程中使用碱或其他添加剂。