Department of Chemistry & Chemical Biology , The University of New Mexico , Albuquerque , New Mexico 87131 , United States.
Sandia National Laboratories , Advanced Materials Laboratory , 1001 University Boulevard SE , Albuquerque , New Mexico 87106 , United States.
J Am Chem Soc. 2018 Jun 27;140(25):7782-7786. doi: 10.1021/jacs.8b03163. Epub 2018 Jun 14.
We disclose a [(PhO)P]/NiBr-catalyzed regioselective β,δ-diarylation of unactivated olefins in ketimines with aryl halides and arylzinc reagents. This diarylation proceeds at remote locations to the carbonyl group to afford, after simple H workup, diversely substituted β,δ-diarylketones that are otherwise difficult to access readily with existing methods. Deuterium-labeling and crossover experiments indicate that diarylation proceeds by ligand-enabled contraction of transient nickellacycles.
我们披露了一种 [(PhO)P]/NiBr 催化的酮亚胺中未活化烯烃与芳基卤化物和芳基锌试剂的区域选择性β,δ-二芳基化反应。这种二芳基化反应发生在远离羰基的位置，得到经过简单 H 处理后，取代基多样的β,δ-二芳基酮，否则用现有方法很难轻易获得。氘标记和交叉实验表明，二芳基化反应是通过配体促进的瞬态镍络合物的收缩来进行的。
