Synthesis and X-ray Crystal Structures of Zinc Complexes Supported by Chelating Ligands: Various Reactions of -Iminopyridines with ZnEt2
Synthesis and X-ray Crystal Structures of Zinc Complexes Supported by Chelating Ligands: Various Reactions of -Iminopyridines with ZnEt2
复制标题
螯合配体负载的锌配合物的合成和 X 射线晶体结构：-亚氨基吡啶与 ZnEt2 的各种反应
DOI：
10.1002/zaac.201800120
复制
发表时间：
2018
影响因子：
1.4
通讯作者：
Li Jianfeng
中科院分区：
文献类型：
--
作者：
Wang Haimang;Guo Zhiqiang;Yang Jihong;Cao Wei;Hua Yupeng;Wei Xuehong;Li Jianfeng
α-亚氨基吡啶（α-IP）是一种重要的氧化还原非无害配体。 α-IPs亚氨基官能团上的取代基对与二乙基锌的反应选择性具有重要影响。对于亚氨基碳上带有氢取代基的α-IP，非大体积N-取代基苯基和2-甲基苯基发生还原反应，而对于空间大的N-取代基2,6-二甲基苯基或2,4,6-三甲基苯基，可以选择性地实现烷基加成和偶联反应。然而，对于亚氨基碳上带有CH3取代基的α-IPs，无论N-取代基是2-甲基苯基还是2,6-二甲基苯基，都会发生去质子化反应。所有产物均通过单晶 X 射线衍射进行分离和表征。还讨论了这些反应的可能机制。
α‐Iminopyridine (α‐IP) is an important redox‐noninnocent ligand. The substituents on the imino function of α‐IPs have important impact on the reaction selectivity with diethylzinc. For the α‐IPs with a hydrogen substituent on the imino carbon, reduction occurred for the non‐bulky N‐substituents phenyl and 2‐methylphenyl groups, whereas alkyl addition and coupling reactions can be selectively achieved for the sterically bulkyN‐substituents 2,6‐dimethylphenyl or 2,4,6‐trimethylphenyl group. However, for the α‐IPs with a CH3substituent on the imino carbon, the deprotonation reaction happened regardless of theN‐substituents of 2‐methylphenyl or 2,6‐dimethylphenyl group. All the products were isolated and characterized by single‐crystal X‐ray diffraction. The possible mechanisms of these reactions were also discussed.