Ligand effects on the chemoselectivity of ortho-metalated rhodium(II) catalyzed alpha-diazo ketone transformations

被引:53
作者
Estevan, F
Lahuerta, P
PerezPrieto, J
Sanau, M
Stiriba, SE
Ubeda, MA
机构
[1] UNIV VALENCIA, FAC QUIM, DEPT QUIM INORGAN, E-46100 BURJASSOT, VALENCIA, SPAIN
[2] UNIV VALENCIA, FAC FARM, DEPT QUIM ORGAN, E-46100 BURJASSOT, VALENCIA, SPAIN
关键词
H INSERTION REACTIONS; INTRAMOLECULAR CYCLOPROPANATION; CARBENE TRANSFORMATIONS; DIAZOCARBONYL COMPOUNDS; MOLECULAR-STRUCTURE; CARBONYL-COMPOUNDS; ORGANIC-SYNTHESIS; DIAZOACETATES; CARBOXYLATES; SELECTIVITY;
D O I
10.1021/om9608162
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Rh-2(OOCR)(2)(PC)(2) complexes (PC = orthometalated phosphines, OOCR = carboxylates) with very polarizable ligands, such as aromatic rings directly joined to the rhodium atoms, control chemoselectivity in competitive metal carbene transformations of cc-diazo ketones. These catalysts have a mixed set of ligands that allows choosing among a big selection of ligands to gradually affect the electronic and steric properties of the catalyst. Their selectivity depends on the electrophilicity of the ligands and the polarizability of the metalated aromatic rings. Thus, Rh-2(OOCR)(2)(PC)(2) compounds [PC = (C6H4)P(CH3)(C6H5), (p-CH3C6H3)P(pCH(3)C(6)H(4))(2), (C6H4)P(C6H5)(2); R = C3F7 or CF3] exhibit an exceptional selectivity for aliphatic C-H insertion over aromatic substitution in catalytic decomposition of 1-diazo-5-methyl-3-phenyl-2-hexanone. Results obtained from these complexes in competitive intramolecular cyclopropanation versus tertiary C-H insertion, cyclopropanation versus aromatic substitution, and C-H insertion versus aromatic substitution are compared with those obtained for other rhodium(II) compounds, such as rhodium(II) caprolactamate (Rh-2(cap)(4)), rhodium(II) perfluorobutyrate, and rhodium(II) acetate.
引用
收藏
页码:880 / 886
页数:7
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