(4S)-4-t-butyldiphenylsilyloxy-2-carbomethoxycyclohex-2-en-1-one | 415928-19-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4S)-4-t-butyldiphenylsilyloxy-2-carbomethoxycyclohex-2-en-1-one
• 英文别名: methyl (3S)-3-[tert-butyl(diphenyl)silyl]oxy-6-oxocyclohexene-1-carboxylate
• CAS: 415928-19-7
• 化学式: C₂₄H₂₈O₄Si
• 分子量: 408.569
• InChiKey: YQGHWHQIOUMQMO-SFHVURJKSA-N

物化性质

• 沸点：
  487.4±45.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.39
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4S)-4-t-butyldiphenylsilyloxy-2-carbomethoxycyclohex-2-en-1-one 在 caesium carbonate 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 生成 (4S,5S,9R,10R,1'R,5'R)-methyl 8-bromo-4-t-butyldiphenylsilyloxy-1,7-dioxo-9-{2''-[5'-(3-furyl)-1'-methyl-2'-oxocyclopent-1'-yl]-eth-1''-yl}-decahydronaphthalene-10-carboxylate
  参考文献：
  名称：

  旨在通过阴离子多环化反应合成不对称的心脏活性类固醇的研究。

  摘要：

  [反应：见正文]研究了阴离子多环化（AP）在构建烯醇内酯类固醇骨架中的应用。2-羧甲氧基-2-环己烯酮Ⅰ与纳扎罗夫试剂Ⅱ的烯醇化物反应，在脱羧和醛醇缩合后，在立体化学控制下得到甾族化合物Ⅲ。

  DOI：

  10.1021/ol027125o
• 作为产物：
  描述：

  (4S)-4-t-butyldiphenylsilyloxy-2-carbomethoxycyclohexan-1-one 在 吡啶 、 双氧水 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 2.0h， 生成 (4S)-4-t-butyldiphenylsilyloxy-2-carbomethoxycyclohex-2-en-1-one
  参考文献：
  名称：

  A Convergent Synthesis of the Cardenolide Skeleton:  Intramolecular Aldol Condensation via Reduction of α-Bromoketones

  摘要：

  Synthesis of the highly biologically valuable cardenolide backbone was achieved via anionic polycyclization. Bromoketone 18, obtained from double-Michael cycloaddition between cyclohexenone 14 and gamma,delta-unsaturated beta-ketoester 16, was efficiently aldolized under reductive conditions. The highly functionalized tetracyclic compound 52 is an important synthetic intermediate that is potentially amenable to natural cardenolide total synthesis.

  DOI：

  10.1021/jo025612b

文献信息

• New Strategy for Convergent Steroid Synthesis
  作者：Olivier Lepage、Pierre Deslongchamps

  DOI：10.1021/jo026676p

  日期：2003.3.1

  We published recently our results on a new and convergent synthesis of natural steroids. The strategy was based on a cycloaddition reaction of Nazarov reagents 2 and 5 with cyclohexenones 1 and 4. In this paper we report results that deal with the synthesis of two new bicyclic Nazarov reagents (13 and 19) and their cycloaddition with two cyclohexenones (1 and 4). These new results constitute an important

  我们最近发表了关于新的和聚合的天然类固醇合成的研究结果。该策略基于Nazarov试剂2和5与环己烯酮1和4的环加成反应。在本文中，我们报告的结果涉及两种新的双环Nazarov试剂（13和19）的合成以及它们与两种环己烯酮的环加成反应（1和4）。这些新结果构成了有关该策略多功能性的重要改进，因为现在可以使用在天然类固醇中发现具有立体化学的四环化合物。
• Nazarov Reagents for Convergent and Expedient Synthesis of New Steroids
  作者：Olivier Lepage、Charles Stone、Pierre Deslongchamps

  DOI：10.1021/ol017274r

  日期：2002.4.1

  [reaction: see text] A new methodology for the convergent synthesis of tetracyclic compounds was developed. Two new bicyclic Nazarov reagents of type II were synthesized, and their cycloaddition with 2-carbomethoxy-2-cyclohexenone I was studied. This cycloaddition afforded new interesting steroidal backbones.

  [反应：见正文]开发了一种收敛合成四环化合物的新方法。合成了两种新的II型双环Nazarov试剂，并研究了它们与2-羰甲氧基-2-环己烯酮I的环加成反应。这种环加成反应提供了新的有趣的甾体骨架。
• A Convergent Synthesis of the Cardenolide Skeleton:  Intramolecular Aldol Condensation via Reduction of α-Bromoketones
  作者：Daniel Chapdelaine、Julie Belzile、Pierre Deslongchamps

  DOI：10.1021/jo025612b

  日期：2002.8.1

  Synthesis of the highly biologically valuable cardenolide backbone was achieved via anionic polycyclization. Bromoketone 18, obtained from double-Michael cycloaddition between cyclohexenone 14 and gamma,delta-unsaturated beta-ketoester 16, was efficiently aldolized under reductive conditions. The highly functionalized tetracyclic compound 52 is an important synthetic intermediate that is potentially amenable to natural cardenolide total synthesis.
• Studies Directed toward Asymmetric Synthesis of Cardioactive Steroids via Anionic Polycyclization
  作者：Zhixiang Yang、Dean Shannon、Vouy-Linh Truong、Pierre Deslongchamps

  DOI：10.1021/ol027125o

  日期：2002.12.1

  [reaction: see text] The use of anionic polycyclization (AP) in constructing the steroidal backbone of cardenolides was investigated. The reaction of 2-carbomethoxy-2-cyclohexenone I with the enolate of Nazarov reagent II gave, after decarboxylation and aldol condensation, steroid III with control of stereochemistry.

  [反应：见正文]研究了阴离子多环化（AP）在构建烯醇内酯类固醇骨架中的应用。2-羧甲氧基-2-环己烯酮Ⅰ与纳扎罗夫试剂Ⅱ的烯醇化物反应，在脱羧和醛醇缩合后，在立体化学控制下得到甾族化合物Ⅲ。