申请人:Hashimoto Shunichi
公开号:US20090227743A1
公开(公告)日:2009-09-10
The present invention relates to a polymer-supported rhodium (II) catalyst and its application, which includes addition reaction to carbon-carbon multiple bond in α-diazocarbonyl compounds, insertion reaction to C—H and X—H (X═N, O, S, Se, Si and the like) bonds, or rearrangement and additional cyclization reaction thereof
A novel insoluble polymer-supported rhodium (II) complex was prepared through a ligand exchange reaction between an insoluble polymer and a rhodium (II) carboxylato complex, wherein the insoluble polymer was prepared by a copolymerization reaction of (i) a styrene derivative with substituted carboxylic acid, (ii) a stylene, and (iii) a linear alkane with both ends substituted by vinylbenzyloxy groups,
Namely, a polymer-supported metal complex catalyst having the following chemical formula 1:
wherein M
1
and M
2
are rhodium, and the like; and X is an oxygen atom, etc; and R
4
is an alkyl group, and the like; and k is 1 to 15%, m is 1 to 5% relative to k+l+m, and l is the remainder; and n is 4 and others; and R
1
is alkyl-2-(4′-alkyloxy phthalimido methyl), etc, R
2
is phenyl, etc; R
3
is 4,4′-(1,3-propyrene-1,3-dioxymethyl)phenyl, etc.
本发明涉及一种
聚合物支撑的二价
铑催化剂及其应用,包括对α-重
氮基化合物中的
碳-
碳多键进行加成反应,对C-H和X-H(其中X = N,O,S,Se,Si等)键进行插入反应,或对其进行重排和附加环化反应。通过不溶性
聚合物与二价
铑羧酸酯配合物之间的
配体交换反应制备了一种新型不溶性
聚合物支撑的
铑(II)配合物,其中不溶性
聚合物是由(i)一种
苯乙烯衍
生物与取代
羧酸、(ii)一种
苯乙烯和(iii)两端取代为
乙烯基苯甲
氧基基团的线性
烷烃进行共聚反应制备的。即,具有以下
化学式1的
聚合物支撑
金属配合物
催化剂:其中M1和M2是
铑等;X是
氧原子等;R4是烷基等;k相对于k+l+m为1至15%,m为1至5%,l为余数;n为4等;R1是烷基-2-(4'-烷
氧基邻
苯二酰亚
甲基)等,R2是
苯基等;R3是4,4'-(1,3-
丙烯-1,3-二
氧甲基)
苯基等。