Ligand Conjugation Directs the Formation of a 1,3-Dihydropyridinate Regioisomer
Ligand Conjugation Directs the Formation of a 1,3-Dihydropyridinate Regioisomer
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配体缀合引导 1,3-二氢吡啶酸酯区域异构体的形成
DOI：
10.1021/acs.inorgchem.0c02847
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发表时间：
2020
影响因子：
4.6
通讯作者：
Berben, Louise A.
中科院分区：
文献类型：
--
作者：
Sherbow, Tobias J.;Parsons, Leo W.;Phan, Nathan A.;Fettinger, James C.;Berben, Louise A.
NAD（P）H的1，4-二氢吡啶异构体的选择性形成通过合成体系中1，4-二氢吡啶配体-金属络合物的选择性形成来反映。在这里，我们证明，配体共轭可用于促进选择性的1，3-二氢吡啶形成。这代表了控制和调整二氢吡啶酸盐形成化学选择性的进步。（I_2P ~（2-）Al（THF）Cl [1; I_2P =双（亚氨基）吡啶; THF =四氢呋喃]与单电子氧化剂（2，2，6，6-四甲基哌啶-1-基）氧基（克里思）反应得到（I_2P ~（2-）Al（克里思）Cl（2），后者可被钠还原为二次还原的配体配合物（I_2P ~（2-）Al（克里思）（3）。化合物2和3作为前体，通过2与3当量的钾金属反应或3与KH反应，高产率和选择性地制备铝负载的1，3-二氢吡啶配合物。
The selective formation of the 1,4-dihydropyridine isomer of NAD(P)H is mirrored by the selective formation of 1,4-dihydropyridinate ligand–metal complexes in synthetic systems. Here we demonstrate that ligand conjugation can be used to promote selective 1,3-dihydropyridinate formation. This represents an advance toward controlling and tuning the selectivity in dihydropyridinate formation chemistry. The reaction of (I2P2–)Al(THF)Cl [1; I2P = bis(imino)pyridine; THF = tetrahydrofuran] with the one-electron oxidant (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) afforded (I2P–)Al(TEMPO)Cl (2), which can be reduced with sodium to the twice-reduced ligand complex (I2P2–)Al(TEMPO) (3). Compounds2and3serve as precursors for high-yielding and selective routes to an aluminum-supported 1,3-dihydropyridinate complex via the reaction of2with 3 equiv of potassium metal or the reaction of3with KH.