π-アリルパラジウムアジド錯体を利用する新触媒反応

概要

論文の詳細を見る
The catalytic reactions involving π-allylpalladium complexes are one of the well-studied and established fields in organometallic chemistry. We have found entirely new types of catalytic transformations through a π-allylpalladium azide complex. The palladium-catalyzed three-component coupling (TCC) reaction of isocyanides, allyl methyl carbonate, and trimethylsilyl azide afforded allyl cyanamides via the π-allylpalladium mimic of Curtius rearrangement. This TCC reaction was further applied for the synthesis of <I>N</I>-cyanoindoles with employing 2-alkynylisocyanobenzenes as a starting material. The palladium-catalyzed TCC reaction of cyano compounds, allyl methyl carbonate, and trimethylsilyl azide also proceeded to give 2-allyltetrazoles regioselectively via the [3+2] cycloaddition between π-allylpalladium azide complex and cyanides. The regiospecific formation of 2-allyl-1, 2, 3-triazoles was observed when the TCC reaction was carried out with utilizing activated alkynes as a staring material instead of cyano compounds.
社団法人有機合成化学協会の論文
2004-07-01