Cross-Coupling between Difluorocarbene and Carbene-Derived Intermediates Generated from Diazocompounds for the Synthesis of <i>gem</i>-Difluoroolefins
作者:Jian Zheng、Jin-Hong Lin、Liu-Ying Yu、Yun Wei、Xing Zheng、Ji-Chang Xiao
DOI:10.1021/acs.orglett.5b03159
日期:2015.12.18
diazocompounds was developed to give gem-difluoroolefins, which constitutes a fast practical pathway to achieve hindered gem-difluoroolefins. The cross-coupling between difluorocarbene and aryl diazoacetates proceeded smoothly in the presence of a copper source, whereas its coupling with diaryl diazomethanes occurred well under metal-free conditions. A mechanism involving a copper–difluorocarbene complex
发展了二氟卡宾与重氮化合物生成的卡宾衍生的中间体之间的交叉偶联,得到了宝石-二氟烯烃,这构成了获得受阻的宝石-二氟烯烃的快速实用途径。在有铜源的情况下,二氟卡宾与芳基重氮乙酸酯之间的交叉偶联反应顺利进行,而其与二芳基重氮甲烷的偶联在无金属条件下发生得很好。提出了一种涉及铜-二氟卡宾络合物的机理。