Madeira Filipe, Veiros Luis F, Alves Luis G, Martins Ana M
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal.
Centro de Química Estrutural, Associação do Instituto Superior Técnico para a Investigação e Desenvolvimento, Av. António José de Almeida nº 12, 1000-043 Lisbon, Portugal.
Molecules. 2023 Dec 7;28(24):7998. doi: 10.3390/molecules28247998.
[(BnCyclam)Y(N(SiMe))] was prepared by reaction of HBnCyclam with Y[N(SiMe)]. The protonation of the macrocycle ligand in [(BnCyclam)Y(N(SiMe))] is observed upon reaction with [HNMe][BPh] leading to the formation of [(HBnCyclam)Y(N(SiMe))][BPh]. DFT analysis of [(BnCyclam)Y(N(SiMe))] showed that the HOMO is located on the anionic nitrogen atoms of the cyclam ring indicating that protonation follows orbital control. Addition of HBnCyclam and H(Bn)Cyclam to a 1:3 mixture of YCl and LiCHSiMe in THF resulted in the formation of [((CHCH)BnCyclam)Y(THF)(µ-Cl)Li(THF)] and [Y{(η-Bn)Cyclam}Li(THF)], respectively. The reaction of HBnCyclam with Y(CHSiMe)(THF) was studied and monitored by a temperature variation NMR experiment revealing the formation of [(BnCyclam)Y(CHSiMe)]. Preliminary catalytic assays have shown that [Y{(η-Bn)Cyclam}Li(THF)] is a very efficient catalyst for the intramolecular hydroamination of 2,2-diphenyl-pent-4-enylamine.
[(BnCyclam)Y(N(SiMe))] 通过 HBnCyclam 与 Y[N(SiMe)] 反应制备而成。[(BnCyclam)Y(N(SiMe))] 与 [HNMe][BPh] 反应时，观察到大环配体发生质子化，生成 [(HBnCyclam)Y(N(SiMe))][BPh]。对 [(BnCyclam)Y(N(SiMe))] 的密度泛函理论 (DFT) 分析表明，最高占据分子轨道 (HOMO) 位于环胺环的阴离子氮原子上，这表明质子化遵循轨道控制。将 HBnCyclam 和 H(Bn)Cyclam 添加到 YCl 和 LiCHSiMe 在四氢呋喃 (THF) 中的 1:3 混合物中，分别生成了 [((CHCH)BnCyclam)Y(THF)(µ-Cl)Li(THF)] 和 [Y{(η-Bn)Cyclam}Li(THF)]。通过变温核磁共振实验研究并监测了 HBnCyclam 与 Y(CHSiMe)(THF) 的反应，结果表明生成了 [(BnCyclam)Y(CHSiMe)]。初步催化试验表明，[Y{(η-Bn)Cyclam}Li(THF)] 是 2,2-二苯基-4-戊烯基胺分子内氢胺化反应的一种非常有效的催化剂。
