Catalytic cross-coupling reaction of esters with organoboron compounds and decarbonylative reduction of esters with HCOONH4: a new route to acyl transition metal complexes through the cleavage of acyl-oxygen bonds in esters.
Catalytic cross-coupling reaction of esters with organoboron compounds and decarbonylative reduction of esters with HCOONH4: a new route to acyl transition metal complexes through the cleavage of acyl-oxygen bonds in esters.
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DOI：
10.1021/jo0492719
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发表时间：
2004-07
期刊：
影响因子：
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通讯作者：
Hiroto Tatamidani;K. Yokota;F. Kakiuchi;N. Chatani
中科院分区：
文献类型：
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作者：
Hiroto Tatamidani;K. Yokota;F. Kakiuchi;N. Chatani
描述了Ru3(CO)12催化酯与有机硼化合物交叉偶联生成酮的反应。各种各样的官能团可以在反应条件下耐受。芳香硼酸盐作为偶联体生成芳基酮。通过使用9-烷基-9- bbn代替硼酸盐，也可以实现酰基-烷基与二烷基酮的偶联。还描述了Ru3(CO)12催化甲酸铵（HCOONH4）对酯类进行脱碳还原生成碳氢化合物的反应。没有产生预期的醛，对照实验表明醛不是转化的中间产物。氢硅烷也可用作还原剂代替HCOONH4。各种各样的官能团对这两个反应都是相容的。这两种催化反应的关键步骤是导向基团促进酯中酰基碳氧键的裂解，从而生成酰基过渡金属烷氧配合物。
The Ru3(CO)12-catalyed cross-coupling reaction of esters with organoboron compounds leading to ketones is described. A wide variety of functional groups can be tolerated under the reaction conditions. Aromatic boronates function as a coupling partner to give aryl ketones. Acyl-alkyl coupling to dialkyl ketones is also achieved by the use of 9-alkyl-9-BBN in place of boronates. The Ru3(CO)12-catalyzed decarbonylative reduction of esters with ammonium formate (HCOONH4) leading to hydrocarbons is also described. No expected aldehydes are produced, and controlled experiments indicate that aldehydes are not intermediate for the transformation. A hydrosilane can also be used as a reducing reagent in place of HCOONH4. A wide variety of functional groups are compatible for both reactions. The key step for both catalytic reactions is the directing group-promoted cleavage of an acyl carbon-oxygen bond in esters, leading to the generation of acyl transition metal alkoxo complexes.