【作者】 张前； 熊涛； 李燕； 赵金钵； 张茜；

【Author】 Qian Zhang;Tao Xiong;Yan Li;Jinbo Zhao;Qian Zhang;Department of Chemistry,Northeast Normal University;

【机构】 东北师范大学化学学院；

【摘要】 氮中心自由基在许多化学及生化过程中起着至关重要的作用,是重要的有机合成中间体。相对于研究比较成熟、应用非常广泛的亲核和亲电胺化反应,自由基胺化反应还远未被充分开发,发展空间广阔。高活性的氮中心自由基物种多是在自由基引发剂作用下产生,反应的选择性差,难以避免的氢原子攫取、歧化等副反应大大限制了基于氮中心自由基构建C-N键方法的应用。比较有价值的反应类型主要集中在分子内胺化反应来构建含氮杂环[1]。我们利用在温和条件下产生氮中心自由基的新策略,发展了基于氮中心自由基的不饱和双键的胺氰化、二胺化、胺氟化、胺氧化、氧化胺化以及炔烃的自由基胺芳化和胺化多官能团化串联反应;发展了无导向基团协助的各种甲苯衍生物苄位C-H键直接胺化反应;实现了酮羰基α位C-H键及无导向基芳烃芳环C-H键与N-H键的直接自由基胺化反应^[2]。更多还原

【Abstract】 Nitrogen-centered radicals play an important role in biological transformations and serve as the versatile synthetic intermediates.Compared with the well established nucleophilic and electrophilic amination reactions,the construction of C-N bonds based on nitrogen-centered radical is less explored,which can be attributed to the harsh conditions required for the generation of nitrogen-centered radicals and their propensity for hydrogen abstraction or engaging in other degradation pathways.[1]Based on the new strategy-generation of nitrogen-centered radical under mild conditions,we developed aminocyanation,aminooxygenation,diamination,aminofluorination and oxidative-amination reactions of unsaturated C-C bonds,aminoarylation and aminative multifunctionalization reaction of alkynes;Directing group-free benzylic C-H amination of toluene derivatives;Radical amination reaction of alpha sp~3 C-H bonds of ketones/directing group free aromatic sp~2C-H bonds and N-H bonds.[2]更多还原