3-(t-butyldimethylsilyl)oxy-2,2-dimethylcyclohexanone | 352424-95-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-(t-butyldimethylsilyl)oxy-2,2-dimethylcyclohexanone
• 英文别名: 3-tert-butyldimethylsilyloxy-2,2-dimethylcyclohexanone；3-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethylcyclohexan-1-one
• CAS: 352424-95-4
• 化学式: C₁₄H₂₈O₂Si
• 分子量: 256.461
• InChiKey: KQNSMSHYITVLQP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3-(t-butyldimethylsilyl)oxy-2,2-dimethylcyclohexanone 在 lithium diisopropyl amide 、 盐酸 、 苯基氯化硒 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 0.25h， 以50%的产率得到5-(t-butyldimethylsilyl)oxy-6,6-dimethyl-2-cyclohexenone
  参考文献：
  名称：

  2,2-Disubstituted analogues of the natural hormone 1α,25-dihydroxyvitamin D 3 : chemistry and biology

  摘要：

  Six new 2, 2-disubstituted analogues of the natural hormone calcitriol have been prepared. Chemical novelty includes (1) the first example of an inverse-electron-demand Diels-Alder cycloaddition using a pyrone diene and a difluorinated vinyl ether dienophile, leading to difluorinated analogues 7 and (2) a conceptually streamlined approach to dimethylated 19-nor analogues 8. Analogues 7a and 8a are similar to calcitriol in terms of in vitro antiproliferative activity, but they are different from calcitriol in terms of transcriptional activity: difluorinated analogue 7a is 2-3 times more active transcriptionally than calcitriol, whereas dimethylated analogue 8a is 7.5 times less active transcriptionally. Whereas the in vivo calcemic activity of difluorinated analogue 7a is similar to that of calcitriol, dimethylated analogue 8a is considerably less calcemic than calcitriol. Dimethylated analogue 8a strongly suppresses parathyroid hormone (PTH) secretion. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(02)00058-5
• 作为产物：
  描述：

  叔丁基二甲硅基三氟甲磺酸酯 、 3-hydroxy-2,2-dimethylcyclohexanone 在 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 3-(t-butyldimethylsilyl)oxy-2,2-dimethylcyclohexanone
  参考文献：
  名称：

  2,2-Disubstituted analogues of the natural hormone 1α,25-dihydroxyvitamin D 3 : chemistry and biology

  摘要：

  Six new 2, 2-disubstituted analogues of the natural hormone calcitriol have been prepared. Chemical novelty includes (1) the first example of an inverse-electron-demand Diels-Alder cycloaddition using a pyrone diene and a difluorinated vinyl ether dienophile, leading to difluorinated analogues 7 and (2) a conceptually streamlined approach to dimethylated 19-nor analogues 8. Analogues 7a and 8a are similar to calcitriol in terms of in vitro antiproliferative activity, but they are different from calcitriol in terms of transcriptional activity: difluorinated analogue 7a is 2-3 times more active transcriptionally than calcitriol, whereas dimethylated analogue 8a is 7.5 times less active transcriptionally. Whereas the in vivo calcemic activity of difluorinated analogue 7a is similar to that of calcitriol, dimethylated analogue 8a is considerably less calcemic than calcitriol. Dimethylated analogue 8a strongly suppresses parathyroid hormone (PTH) secretion. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(02)00058-5

文献信息

• A Negishi cross-coupling reaction enables the total synthesis of (+)-stachyflin
  作者：Franz-Lucas Haut、Klaus Speck、Raphael Wildermuth、Kristof Möller、Peter Mayer、Thomas Magauer

  DOI：10.1016/j.tet.2018.02.048

  日期：2018.6

  present a full account on the development of the total synthesis of the antiviral meroterpenoid (+)-stachyflin. The decalin subunit is rapidly accessed by an exo-selective Diels–Alder reaction, whereas the isonindolinone was synthesized via a highly efficient and practical de novo route starting from dimedone. A challenging sp2–sp3 Negishi cross-coupling reaction enabled construction of the crucial C15–C16

  我们目前就抗病毒类萜（+）-水苏木素的全合成的发展提出了一个完整的说明。的萘烷亚基正在迅速由被访问的外切-选择性狄尔斯-阿尔德反应，而isonindolinone合成通过一高效实用的从头航线从双甲酮开始。具有挑战性的sp 2 –sp 3 Negishi交叉偶联反应使连接芳烃和萘烷亚单位的关键C15–C16键得以构建。为了最终安装顺式-十氢萘骨架，使用了路易斯酸催化的环化反应。
• Strategies for the Total Synthesis of Diverse Bromo-Chamigrenes
  作者：Minxing Shen、Manuel Kretschmer、Zachary G. Brill、Scott A. Snyder

  DOI：10.1021/acs.orglett.6b02478

  日期：2016.10.7

  their unique structures, synthetic efforts toward this collection have been modest. Herein, we outline two strategies to generate their skeletons based on (1) a biomimetic bromonium-induced polyene cyclization using BDSB (Et2SBr·SbCl5Br) and (2) a Diels–Alder reaction which ultimately delivered four members of the class. In addition, X-ray crystallography reveals that one member has a structure in need

  迄今为止，已分离出数十种被称为溴-半胱氨酸的螺环倍半萜。然而，尽管它们具有独特的结构，但对该系列的综合努力却很少。在此，我们概述了以下两种生成骨架的策略：（1）使用BDSB（Et 2 SBr·SBCl 5 Br）仿生溴诱导的多烯环化，以及（2）狄尔斯-阿尔德反应最终产生了该类的四个成员。另外，X射线晶体学表明一个成员具有需要修正的结构。