Wenzel Jonas O, Santos Correa Luis, Schmidt Sarah, Meier Michael A R
Laboratory of Applied Chemistry, Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Kaiserstraße 12, 76131, Karlsruhe, Germany.
Laboratory of Applied Chemistry, Institute of Biological and Chemical Systems-Functional Molecular Systems (IBCS-FMS), Karlsruhe Institute of Technology (KIT), Kaiserstraße 12, 76131, Karlsruhe, Germany.
Sci Rep. 2024 Apr 5;14(1):8055. doi: 10.1038/s41598-024-58615-5.
Terpenes represent a promising renewable feedstock for the substitution of fossil resources in the synthesis of renewable platform chemicals, like diamines. This work describes the synthesis and full characterization of 1,4-p-menthane diamine (1,4-PMD) obtained from α-terpinene (1). A two-step procedure using dibenzyl azodicarboxylate (DBAD) and H as rather benign reagents was employed under comparatively mild conditions. Both C-N bonds were formed simultaneously during a visible-light mediated Diels-Alder reaction, which was investigated in batch or flow, avoiding regioselectivity issues during the amination steps that are otherwise typical for terpene chemistry. Heterogeneously catalyzed quadruple hydrogenation of the cycloadduct (2a) yielded 1,4‑PMD (3). While the intermediate cycloadduct was shown to be distillable, the target diamine can be sublimed, offering sustainable purification methods.
萜类化合物是一种很有前景的可再生原料，可用于替代化石资源来合成可再生平台化学品，如二胺。本文描述了由α-萜品烯（1）制得的1,4-对薄荷烷二胺（1,4-PMD）的合成及全面表征。在相对温和的条件下，采用了一种使用二苄基偶氮二甲酸酯（DBAD）和H作为相对温和试剂的两步法。在可见光介导的狄尔斯-阿尔德反应中同时形成了两个C-N键，该反应在间歇或连续流动条件下进行研究，避免了萜类化学中胺化步骤中典型的区域选择性问题。环加成产物（2a）的多相催化四重氢化反应生成了1,4-PMD（3）。虽然中间环加成产物可蒸馏，但目标二胺可升华，提供了可持续的纯化方法。
