Electrochemical hydrogen isotope exchange of amines controlled by alternating current frequency.
Electrochemical hydrogen isotope exchange of amines controlled by alternating current frequency.
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由交流频率控制的胺的电化学氢同位素交换。
DOI：
10.1039/d3fd00044c
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发表时间：
2023
影响因子：
3.4
通讯作者：
Luo,Long
中科院分区：
文献类型：
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作者：
Behera,Nibedita;Gunasekera,Disni;Mahajan,JyotiP;Frimpong,Joseph;Liu,Zhen-Fei;Luo,Long
在这里，我们报告了一种用于α-C(Sp3)-H胺位上的氢同位素交换的电化学协议。由于四氢异喹啉和四氢吡咯烷在α-C(Sp3)-H胺位上的质子转移(PT)和氢原子转移(HAT)动力学不同，被选为两种模型底物，用于控制不同交流频率下的HIE反应结果。我们发现四氢异喹啉在0赫兹(即在直流(DC)电解条件下)和吡咯烷在0.5赫兹都有最高的氢掺入。产物分布和不同频率的D同位素掺入分析表明，四氢异喹啉的HIE受其缓慢的HAT限制，而吡咯烷的HIE受其α-氨基中间体过氧化的限制。依赖于交流频率的胺类化合物可能被用来实现对药物分子中α-胺位点的选择性标记，这将对制药行业产生重大影响。
Here, we report an electrochemical protocol for hydrogen isotope exchange (HIE) at α-C(sp3)–H amine sites. Tetrahydroisoquinoline and pyrrolidine are selected as two model substrates because of their different proton transfer (PT) and hydrogen atom transfer (HAT) kinetics at the α-C(sp3)–H amine sites, which are utilized to control the HIE reaction outcome at different applied alternating current (AC) frequencies. We found the highest deuterium incorporation for tetrahydroisoquinolines at 0 Hz (i.e., under direct current (DC) electrolysis conditions) and pyrrolidines at 0.5 Hz. Analysis of the product distribution and D isotope incorporation at different frequencies reveals that the HIE of tetrahydroisoquinolines is limited by its slow HAT, whereas the HIE of pyrrolidines is limited by the overoxidation of its α-amino radical intermediates. The AC-frequency-dependent HIE of amines can be potentially used to achieve selective labeling of α-amine sites in one drug molecule, which will significantly impact the pharmaceutical industry.
DOI：
--
发表时间：
2006
期刊：
--
影响因子：
--
作者：
Iroon Polytechniou-
通讯作者：
Iroon Polytechniou-