Sato Yoshihiro, Oonishi Yoshihiro, Mori Miwako
Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
J Org Chem. 2003 Dec 12;68(25):9858-60. doi: 10.1021/jo0353334.
Palladium(0)-catalyzed deconjugative allylation of alkenylidenemalonates and alkylidenemalonates was achieved for the first time. Reactions of dimethyl 2-((E)-but-2-enylidene)malonate with various allylic acetates using LHMDS as a base in DMF in the presence of Pd(2)dba(3) (2.5 mol %) and PPh(3) (10 mol %) proceeded at room temperature to give the corresponding alpha-allylation products in good yields in a regio- and stereoselective manner. This reaction can also be used for allylation of dimethyl ethylidenemalonate or dimethyl 2-((E)-pent-2-enylidene)malonate and give the desired alpha-allylation products in good yields.
首次实现了钯(0)催化的亚烯基丙二酸酯和亚烷基丙二酸酯的去共轭烯丙基化反应。在Pd(2)dba(3)（2.5 mol%）和三苯基膦（10 mol%）存在下，以LHMDS为碱，在DMF中，2-((E)-丁-2-烯叉基)丙二酸二甲酯与各种烯丙基乙酸酯在室温下反应，以区域和立体选择性的方式高产率地得到相应的α-烯丙基化产物。该反应也可用于亚乙基丙二酸二甲酯或2-((E)-戊-2-烯叉基)丙二酸二甲酯的烯丙基化反应，并以高产率得到所需的α-烯丙基化产物。
