有机膦催化炔酮分子间的环化反应研究

Organophosphine catalyzed intermolecular cyclization of acetylenic ketone

小分子膦催化环化反应是构建五/六元碳(杂)环的有机合成方法之一。炔酮作为缺电子反应物,可用作潜在的C2、C3、C4合成子参与环化反应,从而构建多种碳环或杂环化合物。为此,研究在叔膦催化下炔酮作为C2和C3合成子参与分子间[3+2]环化反应,生成环戊烯酮类化合物的情况。试验通过对反应催化剂、溶剂、温度及催化剂用量的考察,对反应条件进行优化。结果表明,以1,2-二氯乙烷为反应溶剂,对甲氧基三苯基膦为催化剂,在60℃条件下反应2 h,可获得良好的收率(73%)。该研究为环戊烯酮类化合物的合成提供了新方法。

The phosphine catalyzed cyclization has become one of organic syntheses for construction of five and six member ring systems.As electron-deficient reactants,acetylenic ketone can be used as potential C2,C3 and C4 synthons to participate in cyclization reactions,for the construction of various carbocyclic or heterocyclic compounds.This paper studied the phosphine catalyzed intermolecular[3+2]cyclization for synthesis of cyclopentenones,in which acetylenic ketone participated as C2 and C3 synthons.The best reaction conditions were achieved through a series of optimization including reaction catalysts,solvents,temperatures as well as catalyst loadings.The best chemical yield,up to 73%,can be obtained by using(p-OMePh)3P as catalyst and DCE as reaction solvent at 60℃ for 2 h.The developed method provides a new methodology for preparation of cyclopentenone compounds.