银催化炔基腙与二氧化碳的羧化环化反应（英文）
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摘要
将二氧化碳作为羰一合成子催化转化成重要的杂环精细化学品的方法学研究受到广泛关注.1,3,4-噁二嗪-2-酮类化合物是一类具有重要生理活性的氮氧杂环化合物,广泛用于医药如钙增敏剂、强心剂、杀菌及除草剂等.传统的合成此类化合物的方法包括环状碳酸酯与肼的反应、肼基甲酸酯化合物的闭环反应等,其反应步骤长,效率低,不够经济绿色.本文开发了一种银催化的炔腙类化合物与二氧化碳羧化环化新反应用于高效合成1,3,4-噁二嗪-2-酮.首先选取苯乙炔基羟乙基腙与二氧化碳的羧化环化反应作为模式反应,筛选出适用于此反应的最优反应条件为:5mol%醋酸银为催化剂, 5 mol%碳酸铯为碱,二氧化碳压力为2.0 MPa,二甲基亚砜为溶剂, 25 oC下反应2 h.炔腙分子中碳氮双键的顺反构型对其羧化反应活性没有影响.当使用化学当量的叔丁醇钾或氢化钠等作为碱时,即使在2.0MPa的二氧化碳存在下,炔腙底物也几乎全部转化成非羧化闭环产物吡唑类化合物.在最优反应条件下,氮原子上烷基取代或未取代的炔腙底物能与二氧化碳高效发生羧化环化反应,以54%–90%的产率得到20多种1,3,4-噁二嗪-2-酮产物.反应放大到克级时依旧能高效进行.产物的X射线单晶衍射及氢核磁NOE实验证实,新形成的碳碳双键为顺式结构.当使用氮原子上芳基取代的炔腙时,由于底物中氮原子的亲核反应活性较差,目标羧化产物产率很低.一价银盐通常在二氧化碳参与的羧化反应中作为路易斯酸催化剂活化碳碳叁键.本文对照实验也证明在此羧化环化反应中银盐具有不可或缺的催化作用.改变反应气氛的实验也验证了1,3,4-噁二嗪-2-酮产物中的羰基来自二氧化碳.氢核磁跟踪实验观察到加入催化量碱能有效促进关键肼基甲酸根中间体的形成.以此为依据,本文提出了包含二氧化碳插入炔腙底物形成肼基甲酸根、羧基氧亲核进攻银盐活化的碳碳叁键形成烯基银中间体、质子化得到1,3,4-噁二嗪-2-酮产物及再生银催化剂及碱的催化反应机理.总之,本文发展了一种银催化的简单易得的炔腙类化合物与二氧化碳的羧化环化新反应,为1,3,4-噁二嗪-2-酮类化合物的合成提供了一种方便高效的方法.
The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver(I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom-economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.
The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver(I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom-economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.
引文
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