Reactivity and selectivity of ortho-metalated Rhodium(II) complexes in C-H insertion reactions of α-diazo compounds

被引:33
作者
Estevan, F
Lahuerta, P
Perez-Prieto, J
Pereira, I
Stiriba, SE
机构
[1] Univ Valencia, Fac Quim, Dept Quim Inorgan, E-46100 Burjassot, Valencia, Spain
[2] Univ Valencia, Fac Farm, Dept Quim Inorgan, E-46100 Burjassot, Valencia, Spain
关键词
D O I
10.1021/om971070q
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Regioselective intramolecular C-H insertion reactions of alpha-diazo beta-keto esters and cc-diazo ketones are mediated by Rh-2[OOCR](4-x)[PC](x), (x = 1, 2; PC = ortho-metalated phosphine; R = CH3, C3F7). In particular, the intramolecular transformation of 1-diazo-5-methyl-3 -propyl-2-hexanone catalyzed by Rh-2[OOCCH3](2)[PC](2) (PC = (C6H4)P(C6H5)(2), head-to-tail (H-T) configuration) afforded only the tertiary C-H insertion product. By comparison, no C-H insertion reaction was promoted by doubly metalated complexes with a head-to-head (H-H) configuration. Rh-2[OOCR](3)[PC] compounds were found to be less suited for these type of reactions.
引用
收藏
页码:3442 / 3447
页数:6
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