A Synthetic Cycle for Heteroarene Synthesis by Nitride Insertion.
A Synthetic Cycle for Heteroarene Synthesis by Nitride Insertion.
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DOI：
10.1002/anie.202213041
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发表时间：
2022-11-14
影响因子：
16.6
通讯作者：
Levin, Mark D.
中科院分区：
文献类型：
--
作者：
Kelly, Patrick Q.;Filatov, Alexander S.;Levin, Mark D.
最近对骨架编辑的兴趣需要继续开发具有转移单个原子能力的试剂类别。末端过渡金属氮化物在单原子转移方面有着巨大的潜力，尽管它们在有机合成中的应用到目前为止还很有限。在这里，我们展示了一个合成周期与相关的详细的机制研究，引发终端过渡金属氮化物的发展作为有价值的单原子转移试剂。具体来说，我们显示[cis-terpyOsNCl 2] PF 6插入氮到茚，以提供异喹啉。每个步骤（插入，芳构化，产品释放，和氮化物再生）的机制研究报告，包括转向中间体，动力学和计算研究的晶体学表征。该合成循环的机理基础为后过渡金属氮化物促进的氮插入杂芳烃合成的进一步发展打开了大门。氮化锇被证明可以将氮插入茚中，得到异喹啉。一个合成周期，以再生的起始氮化物旁边的每一个步骤的机理研究。
Recent interest in skeletal editing necessitates the continued development of reagent classes with the ability to transfer single atoms. Terminal transition metal nitrides hold immense promise for single-atom transfer, though their use in organic synthesis has so far been limited. Here we demonstrate a synthetic cycle with associated detailed mechanistic studies that primes the development of terminal transition metal nitrides as valuable single-atom transfer reagents. Specifically, we show [cis-terpyOsNCl2]PF6 inserts nitrogen into indenes to afford isoquinolines. Mechanistic studies for each step (insertion, aromatization, product release, and nitride regeneration) are reported, including crystallographic characterization of diverted intermediates, kinetics, and computational studies. The mechanistic foundation set by this synthetic cycle opens the door to the further development of nitrogen insertion heteroarene syntheses promoted by late transition metal nitrides. An osmium nitride is shown to insert nitrogen into indenes to afford isoquinolines. A synthetic cycle to regenerate the starting nitride is presented alongside mechanistic studies of each step.
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