Regio- and stereochemistry in the sequential insertion of carbonyl compounds into zirconium-diene complexes
作者:Hajime Yasuda、Takuji Okamoto、Kazushi Mashima、Akira Nakamura
DOI:10.1016/0022-328x(89)88041-6
日期:1989.3
derivatives) were found to undergo regioselective addition with a variety of aldehydes, ketones, esters and acid amides at the sterically more crowded terminal carbon of the ligated diene to give the (Z)-oxazirconacyclo-4-heptenes. Further addition of carbonyl compounds to the resulting oxametallacycle leads to adducts of (E)-1,3-dioxazircona-6-nonene structure when the precursor oxazirconacycloheptene has a
组类型的Zr 4金属-二烯配合物(η-C 5 H ^ 5)2(S-顺式-二烯)和Zr(η-C 5 H ^ 5)2 - (S-反式-二烯)(二烯=丁二烯,发现异戊二烯,戊二烯及其衍生物)在连接的二烯的空间更拥挤的末端碳上与多种醛,酮,酯和酰胺进行区域选择性加成,得到(Z)-氧杂碳环环-4-庚烯。将羰基化合物进一步添加到生成的oxametallacycle中会导致(E)-1,3-dioxazircona-6-nonene结构,当前体恶唑烷并环庚烯在C(5)位置具有较小的氢基团时。高选择性,三组分,顺序添加首先通过用Zr(C 5 H 5)2(二烯)/酯,Zr(C 5 H 5)2(二烯/烯烃和Zr( C 5 -H 5)2(二烯)/炔烃加合物。