2-[[tert-butyl(dimethyl)silyl]oxy-phenylmethyl]cyclohexan-1-one | 475635-11-1

• 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: 2-[[tert-butyl(dimethyl)silyl]oxy-phenylmethyl]cyclohexan-1-one
• CAS: 475635-11-1
• 化学式: C₁₉H₃₀O₂Si
• 分子量: 318.531
• InChiKey: NQPUXTWNVVWDEL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.51
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[[tert-butyl(dimethyl)silyl]oxy-phenylmethyl]cyclohexan-1-one 在 盐酸 作用下， 以 甲醇 为溶剂， 生成 2-(hydroxyphenylmethyl)cyclohexan-1-one
  参考文献：
  名称：

  New effective catalysts for Mukaiyama-aldol and -Michael reactions: bismuth trichloride-metallic iodide systems

  摘要：

  Metallic iodide-activated bismuth(III) chloride efficiently catalyzes the Mukaiyama-Aldol and -Michael reactions. Some examples of reactions of silyl enol ethers derived from acetophenone and cyclohexanone (I and 2, respectively) with aldehydes, ketones, acetals, and alpha-enones are given. The cross-over aldolization between 1 and benzaldehyde in the presence of BiCl3-l.5ZnI2 or BiCl3-1.5SnI2 systems (5 % mol) has been carried out quantitatively at -30 and -78-degrees-C, respectively. For this reaction a similar activation has been also observed with antimony(III) chloride. X-ray patterns of catalytic systems show the formation of bismuth(III) iodide by CI/I-exchange reaction between BiCl3 and metallic iodide (NaI, ZnI2, SnI2,...). These results.have been rationalized with a two-step mechanism in which a key feature seems to be the activating role played by BiI3 toward the cleavage of the Bi-chelate intermediate by the chlorosilane formed. Ultrasound activates significantly the catalytic power of these metallic halide systems.

  DOI：

  10.1021/jo00059a040
• 作为产物：
  描述：

  tert-butyl(cyclohex-1-en-1-yloxy)dimethylsilane 、 苯甲醛 在 [双(三氟甲磺酰基)氨基]三甲基硅烷 作用下， 以 乙醚 为溶剂， 反应 0.33h， 生成 2-[[tert-butyl(dimethyl)silyl]oxy-phenylmethyl]cyclohexan-1-one
  参考文献：
  名称：

  共轭碱在甲硅烷基路易斯酸诱导的向山羟醛反应中的关键作用

  摘要：

  甲硅烷基路易斯酸诱导的向山羟醛反应在其共轭碱的影响下通过每个催化循环进行；低亲核共轭碱-NTf2和-CTf3与相对高亲核-OTf之间存在特别显着的差异。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

  DOI：

  10.1002/ejoc.200500845

文献信息

• IMMOBILIZED CATALYST DIRECTED TO SYNTHETIC CONTROL. CROSS-ALDOL REACTION
  作者：Teruaki Mukaiyama、Hiroshi Iwakiri

  DOI：10.1246/cl.1985.1363

  日期：1985.9.5

  Cross-aldol adducts are stereoselectively formed in good yields by treating acetals or aldehydes and silyl enol ethers in a heterogeneous system with a catalytic amount of polymer-supported trityl perchlorate.

  交叉aldol加成产物以高立体选择性和良好产率形成，通过在异质系统中以聚合物负载的三苯甲基高氯酸盐为催化剂处理缩醛或醛与硅基烯醇醚来实现。
• New role of tin(II) compounds in organic synthesis
  作者：Teruaki Mukaiyama、Shū Kobayashi

  DOI：10.1016/0022-328x(90)85213-i

  日期：1990.2

  new carbon-carbon bond forming reactions by the use of new catalyst systems involving tin(II) compounds are described in this article. The aldol reaction of silyl enol ethers with acetals or aldehydes and the Michael reaction of silyl enol ethers with α,β-unsaturated ketones are catalyzed by the combination of a neutral molecule, trityl chloride, and a weak Lewis acid, tin(II) chloride, under extremely

  本文介绍了通过使用涉及锡（II）化合物的新型催化剂体系进行的三个新的碳-碳键形成反应。甲硅烷基烯醇醚与乙缩醛或醛的醛醇缩合反应和甲硅烷基烯醇醚与α，β-不饱和酮的迈克尔反应通过中性分子，三苯甲基氯和弱路易斯酸氯化锡（II）的组合来催化，在极端温和的条件下。类似地，通过路易斯酸和锡（II）化合物的结合产生活性物质，例如，α，β-不饱和硫代酯与甲硅烷基烯醇醚平稳反应，从而通过联合使用以高收率立体选择性地提供相应的迈克尔加合物氯化锑（V）和三氟甲磺酸锡（II）。第三，基于这种结合概念，开发了一种新的手性启动子。
• Crucial role of the ligand of silyl Lewis acid in the Mukaiyama aldol reactionElectronic supplementary information (ESI) available: experimental section. See http://www.rsc.org/suppdata/cc/b2/b203838b/
  作者：Kazuaki Ishihara、Yukihiro Hiraiwa、Hisashi Yamamoto

  DOI：10.1039/b203838b

  日期：2002.7.11

  The Me3SiX-induced Mukaiyama aldol reaction proceeds through each catalytic cycle under the influence of X-: the silyl group of Me3SiNTf2 does not release from -NTf2 and that of silyl enol ether intermolecularly transfers to the product, while the silyl group of Me3SiOTf remains in the product and that of the silyl enol ether becomes the catalyst for the next catalytic cycle.

  Me3SiX诱导的Mukaiyama羟醛反应在X-的影响下在每个催化循环中进行：Me3SiNTf2的甲硅烷基不会从-NTf2释放，甲硅烷基烯醇醚的分子间转移到产物中，而Me3SiOTf的甲硅烷基仍保留在产物和甲硅烷基烯醇醚的产物成为下一催化循环的催化剂。
• AN EFFICIENT METHOD FOR THE PREPARATION OF<i>THREO</i>CROSS-ALDOLS FROM SILYL ENOL ETHERS AND ALDEHYDES USING TRITYL PERCHLORATE AS A CATALYST
  作者：Teruaki Mukaiyama、Shu Kobayashi、Masahiro Murakami

  DOI：10.1246/cl.1985.447

  日期：1985.4.5

  Threo cross-aldol products are predominantly formed in good yields by treating tert-butyldimethylsilyl enol ethers with aldehydes in the presence of a catalytic amount of trityl perchlorate.

  通过在催化量的高氯酸三苯甲基酯存在下用醛处理叔丁基二甲基甲硅烷基烯醇醚，主要以良好的产率形成苏式交叉羟醛产物。
• Trimethylsilyl trifluoromethanesulfonate-catalyzed aldol reaction of various aldehydes with silyl enol ethers.
  作者：Chisato MUKAI、Satoshi HASHIZUME、Kazuyoshi NAGAMI、Miyoji HANAOKA

  DOI：10.1248/cpb.38.1509

  日期：——

  The aldol reaction of trimethylsilyl enol ethers (1-3) with various aldehydes in the presence of a catalytic amount of trimethylsilyl trifluoromethanesulfonate was investigated. With benzaldehyde (4) the β-hydroxycarbonyl compounds were obtained in good yields. The effect of a substituent on the benzene ring was also examined. Aliphatic aldehydes (11, 13, and 14) were found not to be suitable substrates for this catalytic aldol reaction. On treatment with tert-butyldimethylsilyl enol ethers (30 and 31) under the same conditions, benzaldehydes (4, 5, 7, 8) yielded the corresponding aldol products with good threo-selectivity.

  在三氟甲磺酸三甲基硅酯的催化量存在下，研究了三甲基硅基烯醇醚（1-3）与各种醛的羟醛反应。与苯甲醛（4）反应时，可以得到产率良好的β-羟基羰基化合物。同时还考察了取代基对苯环的影响。发现脂肪醛（11、13和14）不适宜作为这一催化羟醛反应的底物。在相同条件下与叔丁基二甲基硅基烯醇醚（30和31）反应时，苯甲醛（4、5、7、8）能够产生具有良好苏式选择性的相应羟醛产物。