Ruthenium‐ and Copper‐Catalyzed Propargylic Substitution Reactions of Propargylic Alcohol Derivatives with Hydrazones
Ruthenium‐ and Copper‐Catalyzed Propargylic Substitution Reactions of Propargylic Alcohol Derivatives with Hydrazones
复制标题
钌和铜催化的丙炔醇衍生物与腙的丙炔取代反应
DOI：
10.1002/chem.202103287
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Nishibayashi Yoshiaki
中科院分区：
文献类型：
--
作者：
Liu Shiyao;Tanabe Yoshiaki;Kuriyama Shogo;Sakata Ken;Nishibayashi Yoshiaki
钌和铜催化丙炔醇衍生物与N -单取代腙作为环境亲核试剂进行丙炔取代反应，其中N -单取代腙根据不同的催化体系表现出令人瞩目的不同反应活性，在钌催化下作为碳中心亲核试剂产生相应的丙炔烷基化产物。或作为氮中心亲核试剂在铜催化中提供相应的丙炔胺化产物。通过离散傅立叶变换（DFT）计算研究了这两种体系的详细反应途径。丙炔取代产物的进一步转化可得到相应的多取代吡唑作为环化产物，收率较高。
Ruthenium‐ and copper‐catalyzed propargylic substitution reactions of propargylic alcohol derivatives with N‐monosubstituted hydrazones as ambident nucleophiles are achieved in which N‐monosubstituted hydrazones exhibit impressive different reactivities depending on different catalytic systems, behaving as carbon‐centered nucleophiles to give the corresponding propargylic alkylated products in ruthenium catalysis, or as nitrogen‐centered nucleophiles to afford the corresponding propargylic aminated products in copper catalysis. DFT calculations were carried out to investigate the detailed reaction pathways of these two systems. Further transformation of propargylic substituted products affords the corresponding multisubstituted pyrazoles as cyclization products in good to high yields.