New Catalytic System for S−S and Se−Se Bond Addition to Alkynes Based on Phosphite Ligands
作者:Valentine P. Ananikov、Michael A. Kabeshov、Irina P. Beletskaya、Vicktor N. Khrustalev、Mikhail Yu. Antipin
DOI:10.1021/om049082g
日期:2005.3.1
A new catalytic system for the Ar2E2 (E = S, Se) addition to terminal alkynes (HC⋮C−R) has been developed to synthesize bis-element-substituted alkenes Z-H(ArE)CC(EAr)R with high stereoselectivity and yields. Utilizing phosphite ligand P(OiPr)3 allowed solving two major problems of this catalytic reaction: (1) prevent catalyst polymerization and (2) simplify product purification procedures. Key i
已开发出一种用于末端炔烃(HC⋮C-R)加成Ar 2 E 2(E = S,Se)的新催化体系,以合成双元素取代的烯烃Z -H(ArE)C C(EAr)具有高立体选择性和产率的R。利用亚磷酸酯配体P(O i Pr)3可以解决该催化反应的两个主要问题:(1)防止催化剂聚合;(2)简化产物纯化程序。关键中间体反式[Pd(SPh)2(P(O i Pr)3)2 ]和反式[Pd 2(SPh)4(P(O i Pr))3)2 ]通过S-S氧化加成反应合成Pd(0)并通过X射线分析研究。通过31 P NMR光谱确定溶液中单核和双核配合物之间的平衡。除了合成方法的优点外,稳定的亚磷酸酯配体与钯配合物的分离还可以对催化反应进行详细的机理研究。