Sherbow Tobias J, Parsons Leo W T, Phan Nathan A, Fettinger James C, Berben Louise A
Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, United States.
Inorg Chem. 2020 Dec 7;59(23):17614-17619. doi: 10.1021/acs.inorgchem.0c02847. Epub 2020 Nov 20.
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 (IP)Al(THF)Cl [; IP = bis(imino)pyridine; THF = tetrahydrofuran] with the one-electron oxidant (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) afforded (IP)Al(TEMPO)Cl (), which can be reduced with sodium to the twice-reduced ligand complex (IP)Al(TEMPO) (). Compounds and serve as precursors for high-yielding and selective routes to an aluminum-supported 1,3-dihydropyridinate complex via the reaction of with 3 equiv of potassium metal or the reaction of with KH.
NAD(P)H 的 1,4 - 二氢吡啶异构体的选择性形成在合成体系中通过 1,4 - 二氢吡啶酸酯配体 - 金属配合物的选择性形成得以体现。在此，我们证明配体共轭可用于促进选择性 1,3 - 二氢吡啶酸酯的形成。这代表了在控制和调节二氢吡啶酸酯形成化学中的选择性方面取得的进展。(IP)Al(THF)Cl [；IP = 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 (TEMPO) 反应得到 (IP)Al(TEMPO)Cl ()，其可被钠还原为二次还原的配体配合物 (IP)Al(TEMPO) ()。化合物 和 作为高产率和选择性路线的前体，通过 与 3 当量金属钾反应或 与 KH 反应生成铝负载的 1,3 - 二氢吡啶酸酯配合物。
