2-(4-tert-butyldimethylsilyloxybutyl)cyclopentanone | 181641-13-4

• 分子结构分类: 有机化合物
• 英文名称: 2-(4-tert-butyldimethylsilyloxybutyl)cyclopentanone
• 英文别名: 2-(4-tert-butyldimethylsilyloxybutyl)cyclopentan-1-one；2-[4-[Tert-butyl(dimethyl)silyl]oxybutyl]cyclopentan-1-one
• CAS: 181641-13-4
• 化学式: C₁₅H₃₀O₂Si
• 分子量: 270.488
• InChiKey: FOONZCXLJMCPGW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.55
• 重原子数：
  18
• 可旋转键数：
  7
• 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
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(4-tert-butyldimethylsilyloxybutyl)cyclopentanone 在 吡啶 、 四丁基氟化铵 、 溴甲酚绿 、 sodium cyanoborohydride 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 为溶剂， 反应 3.0h， 生成 trans-4-[2-(N-methoxylamino)cyclopentyl]-1-butanol
  参考文献：
  名称：

  Rate Constants for 5-Exo Secondary Alkyl Radical Cyclizations onto Hydrazones and Oxime Ethers via Intramolecular Competition Experiments

  摘要：

  The kinetics for the 5-exo cyclizations of secondary radicals onto various imine accepters (aryl-, alkyl-, and benzoylhydrazones, oxime ethers, etc.) have been determined. The rate constants have been established by competitive "internal radical clock" type cyclizations on the basis of the known rate constants for alkene and N,N-diphenylhydrazone systems. In refluxing benzene (80 degrees C) the rate constants for these 5-exo cyclizations fall within the range of 16 x 10(7) to 4 x 10(7) s(-1) depending on the electron-withdrawing capacity of the imine acceptor (C=NR). The fastest rate constants were observed for the N-benzyoylhydrazone acceptor (cis, 1.2 x 10(8) s(-1)), a value that is very similar to rate constant determined previously for N,N-diphenylhydrazones (cis, 1.1 x 10(8) s(-1)), These rate constants are approximately 200 times faster than those for the corresponding 5-exo cyclization onto alkenes.

  DOI：

  10.1021/jo982017u
• 作为产物：
  描述：

  在 lutidine 、 lithium iodide 作用下， 生成 2-(4-tert-butyldimethylsilyloxybutyl)cyclopentanone
  参考文献：
  名称：

  顺式和反式-1,7,9-三恶二螺[5.1.5.3]十六烷：合成研究

  摘要：

  描述了经由二酮二醇2的热力学螺环化的标题化合物的第一合成。已开发出三种收敛的合成方法以保护2的衍生物，所有这些方法均已转化为反式-3：顺式-3的1.70：1.00混合物。这些研究的实际结果是，二氢吡喃和1,5-戊二醇的标题化合物的总收率分别为28％和32％。

  DOI：

  10.1016/0040-4039(96)01165-3

文献信息

• Diastereoselective Synthesis of Diquinanes and Triquinanes Bearing Vicinal Quaternary Carbon Stereocenters from Acyclic Allene-based Precursors via a Cascade Reaction
  作者：Shuang Li、Pengpeng Zhang、Yuanhe Li、Shumin Lu、Jianxian Gong、Zhen Yang

  DOI：10.1021/acs.orglett.7b01733

  日期：2017.9.1

  A cascade benzenethiol-mediated intramolecular [3 + 2] cycloaddition reaction between an allene and an α,β-unsaturated aldehyde or ester is developed for the diastereoselective synthesis of [3.3.0] bicyclic system bearing two quaternary atoms at their bridgehead positions. Notably, these structurally complex systems can be found in a wide range of natural products.

  开发了级联苯硫醇介导的分子间[3 + 2]环内加成反应，用于烯丙基和α，β-不饱和醛或酯的非对映选择性合成[3.3.0]双环系统，在其桥头位置带有两个季原子。值得注意的是，这些结构复杂的系统可以在多种天然产物中找到。
• Facile Construction of the Tricyclo[5.2.1.0^1,5]decane Ring System by Intramolecular Double Michael Reaction:  Highly Stereocontrolled Total Synthesis of (±)-8,14-Cedranediol and (±)-8,14-Cedranoxide
  作者：Masataka Ihara、Kei Makita、Kiyosei Takasu

  DOI：10.1021/jo981996n

  日期：1999.2.1

  It was observed that the synthesis of tricyclo[5.2.1.0(1,5)]decane 10 can be performed effectively by the intramolecular double Michael reaction of 5-(5-methoxycarbonyl-4-pentenyl)-2-cyclopenten-1-one (9). Highly stereocontrolled total syntheses of(+/-)-8, 14-cedranediol (2) and (+/-)-8,14-cedranoxide (1) were accomplished by the application of this methodology. Heating 5-(1,5-dimethyl-5-ethoxycarbonylpent-4-enyl)-2-cyclopenten-1-one (15) with TMSCl, Et3N, and ZnCI2 in o-dichlorobenzene at 150 degrees C provided (+/-)-(1R*, 2R*, 5R*, 6R*, 7S*)-2,6-dimethyl-6-ethoxycarbonyltricyclo[5.2.1.0(1,5)]- decan-9-one (16) as a single isomer. The product 16 was stereoselectively converted into the above cedranoids 2 and 1 through ring expansion chemistry.