Jadhav Appaso Mahadev, Gawade Sagar Ashok, Vasu Dhananjayan, Dateer Ramesh B, Liu Rai-Shung
Department of Chemistry, National Tsing Hua University, Hsinchu, 30013 (Taiwan), Fax: (+886) 3-5711082.
Chemistry. 2014 Feb 10;20(7):1813-7. doi: 10.1002/chem.201304322. Epub 2014 Jan 8.
Catalytic 1,4-dioxo functionalizations of 3-en-1-ynes to (Z)- and (E)-2-en-1,4-dicarbonyl compounds are described. This regioselective difunctionalization was achieved in one-pot operation through initial alkyne hydration followed by in situ Selectfluor oxidation. The presence of pyridine alters the reaction chemoselectivity to give 4-hydroxy-2-en-1-carbonyl products instead. A cooperative action of pyridine and Zn(II) assists the hydrolysis of key oxonium intermediate.
描述了将3-烯-1-炔催化1,4-二氧官能化制备(Z)-和(E)-2-烯-1,4-二羰基化合物的方法。这种区域选择性双官能化反应通过炔烃的水合反应起始，随后原位进行Selectfluor氧化，在一锅反应中实现。吡啶的存在改变了反应的化学选择性，生成4-羟基-2-烯-1-羰基产物。吡啶与Zn(II)的协同作用促进了关键的氧鎓中间体的水解。
