钌螯合的2-吡啶酚胺的多种功能化：氧合，脱氢，环化和N-脱烷基。,Inorganic Chemistry

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钌螯合的2-吡啶酚胺的多种功能化：氧合，脱氢，环化和N-脱烷基。
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-01-07 , DOI: 10.1021/acs.inorgchem.9b03065
Sanjib Panda ₁ , Arijit Singha Hazari ₁ , Manish Gogia ₁ , Goutam Kumar Lahiri ₁

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金属配位的2-吡啶甲基胺（PA）衍生物在碱性条件下与金属前体[RuII（Cl）（H）（CO）（PPh3）3]反应时，已引入“化学无毒”。实际上，这是根据PA主链上的胺氮（Namine）和亚甲基中心（Cα）的微调而容易形成的金属化酰胺，亚胺，环环吡咯和N-脱烷基同类物。当PA的N胺取代基从芳基转变为亲电的戊-3-烯-2-酮部分时，它会在1中生成氧化的L1'，并在4生成环化的L4'。另一方面，将取代基置于PA的Cα位置会改变其反应性，从而导致脱氢（2/3）或N-脱烷基化（6）过程。金属化的PA的发散反应性分布被认为是通过常见的双阴离子中间体进行的。此外，在存在外部亲电试剂例如苄基溴或亚甲基碘的情况下，已经举例说明了配位PA的CH键官能化与配体交换过程的竞争情况。结合过渡态（TS）理论，通过它们的晶体结构和光谱特征解决了产物形成的验证以及对反应路径的阐明。

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Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation.

"Chemical noninnocence" of metal-coordinated 2-picolylamine (PA) derivatives has been introduced upon its reaction with the metal precursor [RuII(Cl)(H)(CO)(PPh3)3] under basic conditions. This in effect leads to the facile formation of metalated amide, imine, ring-cyclized pyrrole, and an N-dealkylated congener based on the fine-tuning of an amine nitrogen (Namine) and a methylene center (Cα) at the PA backbone. It develops oxygenated L1' in 1 and cyclized L4' in 4 upon switching of the Namine substituent of PA from aryl to an electrophilic pent-3-en-2-one moiety. On the other hand, imposing the substituent at the Cα position of PA modifies its reactivity profile, leading to a dehydrogenation (2/3) or N-dealkylation (6) process. The divergent reactivity profile of metalated PA is considered to proceed through a common dianionic intermediate. Further, a competitive scenario of C-H bond functionalization of coordinated PA versus the ligand-exchange process has been exemplified in the presence of external electrophile such as benzyl bromide or methylene iodide. Authentication of the product formation as well as elucidation of the reaction pathway has been addressed by their crystal structures and spectroscopic features in conjunction with the transition-state (TS) theory.

更新日期：2020-01-07

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