Air-Stable, Compact, Caged Trialkylphosphines (SMAPs): Synthesis, Properties and Applications to Homogeneous and Heterogeneous Catalysis
Air-Stable, Compact, Caged Trialkylphosphines (SMAPs): Synthesis, Properties and Applications to Homogeneous and Heterogeneous Catalysis
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空气稳定、紧凑、笼状三烷基膦 (SMAP)：合成、性质及其在均相和多相催化中的应用
DOI：
10.1002/chin.201018233
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发表时间：
2010
期刊：
影响因子：
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通讯作者：
M. Sawamura
中科院分区：
文献类型：
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作者：
M. Sawamura
介绍了以分子或二氧化硅为载体的超致密笼状三烷基膦(SMAP)的合成、性质及其在过渡金属催化中的应用。新的磷化氢是空气稳定的，尽管它们具有强烈的富电子特性。可溶性膦Ph-SMAP在Rh催化的酮硅氢加成和氢化反应中表现出良好的配位体性能。二氧化硅负载的SMAP(SiO_2-SMAP)表现出一种独特的配位行为，形成1：1的P-金属络合物，这似乎是产生高活性催化中心的平台。结果表明，SiO_2-SMAP催化的Rh催化的二叔丁基酮等受阻的酮的硅氢化和氢化反应以及红外催化的官能化芳烃的直接邻位硼化反应具有较宽的底物范围。图1.SMAP和相关的P供体配体。图2.固相支撑的SMAP配体催化作用。自组装的单层膦[Au]-SMAP(9)的化学将在其他地方描述。2.亲本可溶性SMAP配体：pH-SMAP(1a)
Synthesis, properties and applications to transition metal catalysis of extremely compact, caged trialkylphosphines (SMAPs) in the form of molecules or silica–supported materials are described. The new phosphines are air–stable despite their strongly electron–rich character. Soluble phosphine Ph–SMAP showed high ligand performance in the Rh–catalyzed hydrosilylation and hydrogenation of ketones. The silica–supported SMAP (Silica–SMAP) displayed a unique coordination behavior to form 1:1 P–metal complexes, which appeared to be useful as platforms to create highly active catalytic centers. As a result, Silica–SMAP enabled the Rh–catalyzed hydrosilylation and hydrogenation of extremely hindered ketones such as di–tert–butyl ketone as well as Ir–catalyzed directed ortho–borylation of functionalized arenes with a broad substrate scope. Figure 1. SMAP and related P–donor ligands. Figure 2. Solid–supported SMAP ligands. catalysis. The chemistry of the self–assembled monolayer phosphine [Au]–SMAP (9) will be described elsewhere. 2. Parent Soluble SMAP Ligand: Ph–SMAP (1a)
Shinji Murai：“Co_2(CO)_8－乙缩醛与氢硅烷和一氧化碳的催化反应”
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