Syntheses are reported for tripyridine macrocycles 2 and 3 and some of their alkyl derivatives. The macrocycles are designed to stabilize to various extents coordinated d(8) metal precursors and d(6) alkane oxidative addition products (Pt(IV)), therefore allowing favorable kinetics and thermodynamics of (e.g., Pt(II)) the cleavage of substrate H-C(sp(3)) bonds. Both the Chichibabin protocol and oxidative
报道了三
吡啶大环2和3及其一些烷基衍
生物的合成。大环被设计为在不同程度上稳定配位的d(8)
金属前体和d(6)
烷烃氧化加成产物(Pt(IV)),因此允许(例如Pt(II))裂解的有利动力学和热力学。底物HC(sp(3))键。Chichibabin协议和
碘化
铜(I)对碳负离子的氧化偶联都用于大环化步骤。
单质子和双质子化的2的晶体结构在大环中建立原子连接,并揭示了在溶液NMR中由于快速质子迁移而被掩盖的结构特征。