Aldehyde decarbonylation catalysis under mild conditions

被引:146
作者
Beck, CM
Rathmill, SE
Park, YJ
Chen, JY
Crabtree, RH
Liable-Sands, LM
Rheingold, AL
机构
[1] Yale Univ, Dept Chem, New Haven, CT 06511 USA
[2] Univ Delaware, Dept Chem, Newark, DE 19716 USA
关键词
D O I
10.1021/om9905106
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reaction of [RhCl(NBD)](2) with 2.0 equiv of triphos (triphos = bis(2-diphenylphosphinoethyl)phenylphosphine; NBD = bicyclo[2.2.1]hepta-2,5-diene) in THF solution at room temperature affords [Rh(NBD)(triphos)][Cl] (4a), which was isolated as [Rh(NBD)(triphos)][SbF6] (4b) in 67% yield. Treatment of 4b with aqueous formaldehyde in THF solution; at 80 degrees C forms [Rh(CO)(triphos)][SbF6] (2a), which reversibly binds a second equivalent of CO(g) to give [Rh(CO)(2)(triphos)][SbF6] (2b). The complex [Rh(CO)(triphos)][SbF6] has been found to be an effective aldehyde decarbonylation catalyst for primary and aryl aldehydes at temperatures as low as that of refluxing dioxane, with little or no undesirable side products resulting from beta elimination or radical rearrangement.
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页码:5311 / 5317
页数:7
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