MoCl5参与的芳香化合物的C-H活化及原位C-C键偶联反应

研究了MoC l5参与的芳香族化合物C—H键活化及原位C—C键偶联反应,方法不用预先制备芳卤和芳香族金属化合物,用取代苯原位高选择性地合成了一系列4,4′-偶联产物(如:4,4′-二甲氧基联苯,4,4′-二苯氧基联苯,3,3′-二甲基-4,4′-二甲氧基联苯,2,3,2,′3′-四氢-5,5′-二苯并呋喃,3,3′-二氢-2,2′-二甲基-5,5′-二苯并呋喃等),并对产物的结构采用核磁共振和单晶X射线衍射测试技术进行了表征。

芳香碳氢键的活化官能化研究进展

目前已发现多种过渡金属络合物可以实现芳香C—H键的活化.例如Pd,Ru,Rh,Cu,Ni,Fe等的络合物都能够实现导向或非导向的各种芳香C—H键活化官能化.对近年来过渡金属催化的芳香C—H键活化构建C—C键反应进展进行了综述.

Synthesis and Characterization of Osmium Polycyclic Aromatic Complexes via Nucleophilic Reactions of Osmapentalyne

Treatment of osmapentalyne [Os { ≡C-C（COOMe）=CH-C =CH-C（PPh3） =CH-}Cl（PPh3）2]＋ BF4-with arylamines in the presence of Cs2CO3 produced osmium-bridged polycyclic aromatic complexes.In this reaction,metal carbyne of osmapentalyne was first attacked by nucleophiles,followed by a C-H oxidative addition.The UV-Vis spectra of these osmium-bridged polycyclic aromatic complexes were measured.The result shows that these osmium-bridged polycyclic aromatic complexes have broad absorption in the UV-Vis region up to 650 nm.

Phosphine-catalyzed acyl-transfer of heteroaryl ketones for the construction of N-fused heterocycles

An inexpensive phosphine catalyst was used effectively for a transition-metal-free acyl-transfer of N-containing heteroaryl ketones for the rapid synthesis of N-fused heterocycles.The key pre-aromatic spirocyclic intermediate initialized by the single electron transfer(SET)process of Togni's reagentⅡpromoted by the tertiary phosphine resulted in an intriguing and alternative tactic for the cleavage of C–C bonds.By using inexpensive tertiary phosphine as the catalyst,this skeleton-reorganizing approach of N-containing heteroaryl ketones allows a streamlined assembly of complex N-fused heterocycles with broad functional group tolerance.

基于N-亚硝基导向的芳烃C(sp^(2))—H键官能团化研究进展

近年来,N-亚硝基通过与过渡金属螯合协同活化芳烃C(sp^(2))—H键,成功构建了C—C键和C—杂原子键的例子已有报道.它基于内部N—N键的氧化断裂,在反应过程中无需添加外部氧化剂,反应结束后可自行离去,发展成为一种新型高效的导向基团,受到了研究者的广泛关注.总结了基于N-亚硝基导向的芳烃C(sp^(2))—H键官能团化的最新研究进展.

直接活化芳香C—H键构建芳香C—N键的研究进展

芳香C—N键广泛存在于药物、活性天然产物和农药中,其构建方法是目前合成热点之一.芳香C—H键到芳香C—N键的转化是重要的有机转化类型,这种转化是构成芳胺的一种高效方法.这种直接转化具有原子经济性,可持续发展性以及环境友好的特点.主要以芳香C—H键的氮宾插入和氧化胺化为主线,综述了近十年来该领域的研究进展.