4-(tert-butyldimethylsilanyloxy)-4-(4'-nitrophenyl)-2-butanone | 673492-37-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(tert-butyldimethylsilanyloxy)-4-(4'-nitrophenyl)-2-butanone
• 英文别名: (4RS)-4-(tert-butyldimethylsilyloxy)-4-(4-nitrophenyl)butan-2-one；4-(tert-butyldimethylsilyloxy)-4-(4-nitrophenyl)butan-2-one；4-[Tert-butyl(dimethyl)silyl]oxy-4-(4-nitrophenyl)butan-2-one
• CAS: 673492-37-0
• 化学式: C₁₆H₂₅NO₄Si
• 分子量: 323.464
• InChiKey: PVIKYLWPPBVSGW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.64
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-(tert-butyldimethylsilanyloxy)-4-(4'-nitrophenyl)-2-butanone 在 三氟甲磺酸三甲基硅酯 、 lutidine 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 生成 1-fluoro-4-hydroxy-4-(4'-nitrophenyl)-butan-2-one
  参考文献：
  名称：

  Unusual reversal of regioselectivity in antibody-mediated aldol additions with unsymmetrical methyl ketones

  摘要：

  A catalytic regio- and enantioselective aldol reaction of various unsymmetrical methyl ketones with para-nitrobenzaldehyde has been developed using aldolase antibodies as the catalysts. It has been found that the sense and level of regioselectivity for the reactions catalysed by antibody 38C2 and 33F12 are highly dependent on the structure of both the donor and the acceptor but in contrast, antibodies 84G3 and 93F3 catalyse the exclusive formation of the linear regioisomer independent of the structure of the reactants examined. The level of enantiocontrol is very high for most reactions. Both linear aldol enantiomers could be accessed through aldol or retro-aldol reactions using the same antibody. Theoretical studies on regioisomeric alpha- and beta-heteroatom substituted enamines derived from unsymmetrical ketones suggest that most of the linear aldol products formed in the presence of antibodies 84G3 and 93F3 must be formed from intermediate enamines which are not the thermodynamically most favourable. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.10.115
• 作为产物：
  描述：

  1-(4-硝基苯基)-3-氧代-1-丁醇 、 叔丁基二甲基氯硅烷 在 吡啶 、 silver nitrate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 以93%的产率得到4-(tert-butyldimethylsilanyloxy)-4-(4'-nitrophenyl)-2-butanone
  参考文献：
  名称：

  β-烷氧基甲基酮在硼介导的羟醛反应中的1,5-不对称诱导

  摘要：

  在β-三氯甲基-β-烷氧基和β-三氟甲基-β-烷氧基甲基酮与非手性醛的硼介导的醛醇缩合反应中获得了良好水平的底物控制的1,5-顺式立体诱导-烷氧基保护基（TBS或PMB）。在β-芳基-β-烷氧基甲基酮的硼醇醛缩合反应的情况下，仅在β-OPMB基团下获得具有高水平的非对映选择性的1，5-抗加合物。

  DOI：

  10.1021/jo8009165

文献信息

• The Influence of a β-Electron Withdrawing Substituent in Aldol Reactions of Methylketone Boron Enolates
  作者：Luiz C. Dias、Anderson A. de Marchi、Marco. A. B. Ferreira、Andrea M. Aguilar

  DOI：10.1021/ol702204h

  日期：2007.11.1

  We wish to describe here that good levels of substrate-based, 1,5-syn-stereocontrol could be achieved in the boron-mediated aldol reactions of beta-trichloromethyl methylketones with achiral aldehydes, independent of the nature of the beta-alkoxy protecting group.
• 1,5-Asymmetric Induction in Boron-Mediated Aldol Reactions of β-Alkoxy Methylketones
  作者：Luiz C. Dias、Anderson A. de Marchi、Marco A. B. Ferreira、Andrea M. Aguilar

  DOI：10.1021/jo8009165

  日期：2008.8.1

  Good levels of substrate-controlled, 1,5-syn-stereoinduction are obtained in boron-mediated aldol reactions of β-trichloromethyl-β-alkoxy and β-trifluoromethyl-β-alkoxy methylketones with achiral aldehydes, independent of the nature of the β-alkoxy protecting group (TBS or PMB). In the case of boron aldol reactions of β-aryl-β-alkoxy methylketones, the 1,5-anti-adducts were obtained with high levels

  在β-三氯甲基-β-烷氧基和β-三氟甲基-β-烷氧基甲基酮与非手性醛的硼介导的醛醇缩合反应中获得了良好水平的底物控制的1,5-顺式立体诱导-烷氧基保护基（TBS或PMB）。在β-芳基-β-烷氧基甲基酮的硼醇醛缩合反应的情况下，仅在β-OPMB基团下获得具有高水平的非对映选择性的1，5-抗加合物。
• Unusual reversal of regioselectivity in antibody-mediated aldol additions with unsymmetrical methyl ketones
  作者：V Maggiotti、S Bahmanyar、M Reiter、M Resmini、K.N Houk、V Gouverneur

  DOI：10.1016/j.tet.2003.10.115

  日期：2004.1

  A catalytic regio- and enantioselective aldol reaction of various unsymmetrical methyl ketones with para-nitrobenzaldehyde has been developed using aldolase antibodies as the catalysts. It has been found that the sense and level of regioselectivity for the reactions catalysed by antibody 38C2 and 33F12 are highly dependent on the structure of both the donor and the acceptor but in contrast, antibodies 84G3 and 93F3 catalyse the exclusive formation of the linear regioisomer independent of the structure of the reactants examined. The level of enantiocontrol is very high for most reactions. Both linear aldol enantiomers could be accessed through aldol or retro-aldol reactions using the same antibody. Theoretical studies on regioisomeric alpha- and beta-heteroatom substituted enamines derived from unsymmetrical ketones suggest that most of the linear aldol products formed in the presence of antibodies 84G3 and 93F3 must be formed from intermediate enamines which are not the thermodynamically most favourable. (C) 2003 Elsevier Ltd. All rights reserved.