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Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones
Published on: February 7, 2019
Activation of Pyrazines by a Mg-Mg-bonded Compound: Reduction, Homocoupling, and Formation of Metallomacrocycles
Zhenzhou Sun1, Yongsheng Li1, Li Yang1
1Key Laboratory of Medicinal Molecule Science and Pharmaceutics Engineering of Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.
Abstract:
The α-diimine-ligated Mg-Mg-bonded compound [K(THF)3]2[LMg-MgL] (1, L = [(2,6-iPr2C6H3)NC(CH3)]22-) can effectively promote the reduction of pyrazine (Pyz) and derivatives under ambient conditions. Reaction of 1 with 1 equiv of pyrazines (Pyz, 2-MePyz, and 2,5-Me2Pyz) caused two-electron reduction of pyrazines to the dianion (RnPyz2-), which bridges two [LMg(II)] fragments to yield dinuclear complexes [K(THF)2]2[L2-(THF)MgII(μ-RnPyz2-)MgII(THF)L2-] (2-4). When 2 equiv of pyrazine substrates were used, the tetranuclear square complexes, featuring pyrazine radical anions (2,3-Me2Pyz)•- (5) or reductive C-C coupling of Pyz (6), were isolated. Moreover, in the dinuclear complex [L•-MgII(μ-Phz2-)MgIIL•-] (8), the original dianion of α-diimine, L2-, was oxidized to a monoanion (L•-), and phenazine (Phz) was reduced to a dianion.
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