Aldehyde decarbonylation catalysis under mild conditions
Aldehyde decarbonylation catalysis under mild conditions
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DOI：
10.1021/om9905106
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发表时间：
1999-12-06
期刊：
影响因子：
2.8
通讯作者：
Rheingold, AL
中科院分区：
文献类型：
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作者：
Beck, CM;Rathmill, SE;Rheingold, AL
[RhCl(NBD)](2) 与 2.0 当量 triphos（triphos = 双(2-二苯基膦乙基)苯基膦；NBD = 双环[2.2.1]七-2,5-二烯）在 THF 溶液中在室温下反应，得到 [Rh(NBD)(triphos)][Cl] (4a)，将其分离为 [Rh(NBD)(triphos)][SbF6] (4b)，产率 67%。用甲醛水溶液的THF溶液处理4b；在 80°C 时形成 [Rh(CO)(triphos)][SbF6] (2a)，它可逆地结合第二个当量的 CO(g)，得到 [Rh(CO)(2)(triphos)][SbF6] (2b)。复合物 [Rh(CO)(triphos)][SbF6] 被发现是伯醛和芳基醛的有效醛脱羰催化剂，温度低至二恶烷回流温度，几乎没有或没有由 β 消除或自由基重排产生的不良副产物。
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.