School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640 (P.R. China).
Angew Chem Int Ed Engl. 2014 Dec 22;53(52):14485-9. doi: 10.1002/anie.201405058. Epub 2014 Nov 25.
A novel strategy involving Cu-catalyzed oxidative transformation of ketone-derived hydrazone moiety to various synthetic valuable internal alkynes and diynes has been developed. This method features inexpensive metal catalyst, green oxidant, good functional group tolerance, high regioselectivity and readily available starting materials. Oxidative deprotonation reactions were carried out to form internal alkynes and symmetrical diynes. Cross-coupling reactions of hydrazones with halides and terminal alkynes were performed to afford functionalized alkynes and unsymmetrical conjugated diynes. A mechanism proceeding through a Cu-carbene intermediate is proposed for the CC triple bond formation.
一种新型策略涉及酮衍生腙部分的 Cu 催化氧化转化为各种合成有价值的内部炔烃和二炔烃。该方法具有价格低廉的金属催化剂、绿色氧化剂、良好的官能团耐受性、高区域选择性和易得的起始原料。氧化脱质子反应形成内部炔烃和对称二炔烃。腙与卤化物和末端炔烃的交叉偶联反应得到官能化炔烃和非对称共轭二炔烃。提出了一种通过 Cu-卡宾中间体进行 CC 三键形成的机制。
