(S)-4-<(t-butyldimethylsilyl)oxy>-3-methyl-2-cyclohexenone | 136611-25-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-4-<(t-butyldimethylsilyl)oxy>-3-methyl-2-cyclohexenone
• 英文别名: (4S)-4-[(tert-butyldimethylsilyl)oxy]-3-methyl-cyclohex-2-en-1-one；(S)-4-[(tert-butyldimethylsilyl)oxy]-3-methyl-cyclohex-2-en-1-one；(4S)-4-(tert-butyldimethylsilyloxy)-3-methyl-cyclohex-2-enone；(S)-4-[(t-butyldimethylsilyl)oxy]-3-methyl-2-cyclohexenone；(4S)-4-[tert-butyl(dimethyl)silyl]oxy-3-methylcyclohex-2-en-1-one
• CAS: 136611-25-1
• 化学式: C₁₃H₂₄O₂Si
• 分子量: 240.418
• InChiKey: KULLMVZATQYVNT-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.69
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 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：

  (S)-4-<(t-butyldimethylsilyl)oxy>-3-methyl-2-cyclohexenone 在 硼烷四氢呋喃络合物 、 copper(I) bromide dimethylsulfide complex 作用下， 以 四氢呋喃 为溶剂， 反应 24.75h， 生成 (3S,4S)-4-(tert-butyldimethylsilyloxy)-3-(2-hydroxyethyl)-3-methyl-cyclohexanol
  参考文献：
  名称：

  威维他汀支持研究：芳基铅（IV）偶联反应的扩展和限制

  摘要：

  描述了有关welwistatin系统总合成的最新支持研究。目标步骤涉及空间需要的芳基和碳酸偶联剂的铅介导的芳基化，以建立高度拥挤的四环核结构。键入7 β酮酯和β酮腈成功芳基化与各种被卤素-硼-铅交换序列生成邻位和间位取代的芳基铅化合物。化合物的烯醇化物15，19，和25，邻近该芳基化位点，每个轴承的全碳季中心，未能耦合。

  DOI：

  10.1021/jo071156l
• 作为产物：
  描述：

  (-)-4-acetoxy-3-methyl-2-cyclohexen-1-one 在 咪唑 、 甲醇 、 sodium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 (S)-4-<(t-butyldimethylsilyl)oxy>-3-methyl-2-cyclohexenone
  参考文献：
  名称：

  通过4-乙酰氧基-3-甲基-2-环己烯酮的酶催化酯水解合成旋光性环己烯醇衍生物

  摘要：

  光学活性的环己烯醇衍生物9a - 9d和10a - 10c是由（-）- 6合成的，后者是通过外消旋8的酯水解得到的。描述了合成紫杉烷骨架的尝试。

  DOI：

  10.1016/s0040-4020(01)86539-x

文献信息

• Asymmetric Total Synthesis of Glycinoeclepin A: Generation of a Novel Bridgehead Anion Species
  作者：Yasuhiro Shiina、Yoshihide Tomata、Masaaki Miyashita、Keiji Tanino

  DOI：10.1246/cl.2010.835

  日期：2010.8.5

  The asymmetric total synthesis of glycinoeclepin A, a hatch-stimulating agent of the soybean cyst nematode, was accomplished on the basis of a cyclopentene annulation for constructing the CD ring m...

  大豆胞囊线虫的孵化刺激剂甘氨酸环素 A 的不对称全合成是在环戊烯环化的基础上完成的，用于构建 CD 环...
• Straightforward Enantioselective Synthesis of Both Enantiomers of Karahana Lactone Using a Domino Ring-Closure Sequence
  作者：Jean-Marie Galano、Gérard Audran、Honoré Monti

  DOI：10.1016/s0040-4020(00)00645-1

  日期：2000.9

  straightforward enantioselective synthesis of both enantiomers of karahana lactone is described starting from enantiopure (R) or (S)-4-hydroxy-3-methyl-cyclohex-2-en-1-one. The key step of the sequence is an acid-induced domino reaction with three pathways running. Because of the first description of karahana lactone as a solid, the structure was secured by X-ray structural analysis.

  从对映纯（R）或（S）-4-羟基-3-甲基-环己基-2-en-1-one开始描述卡拉汉纳内酯的两种对映体的直接对映选择性合成。序列的关键步骤是酸诱导的多米诺骨牌反应，具有三个运行路径。由于卡拉汉纳内酯为固体的首次描述，因此通过X射线结构分析确定了结构。
• Chemoenzymatic Taxanes Approach Using Both Enantiomers of the Same Building Block. 2. Taxol CD Ring Unit
  作者：Jean-Pierre Uttaro、Gérard Audran、Honoré Monti

  DOI：10.1021/jo050039s

  日期：2005.4.1

  The enantioselective synthesis of the Taxol CD ring unit has been achieved starting from an enantiopure building block, the enantiomer of those previously utilized in the synthesis of the A ring unit. The key features of the present synthesis are astute use of both enantiomers of the same building block and complete control in the construction of five consecutive chiral centers.
• Scalable Total Synthesis of Acremolactone B
  作者：Mengyu Ba、Fengqi He、Lu Ren、William Whittingham、Peng Yang、Ang Li

  DOI：10.1002/anie.202314800

  日期：——

  Acremolactone B is a pyridine‐containing azaphilone‐type polyketide with herbicidal activity. We developed an aza‐6π electrocyclization−aromatization strategy to construct the tetrasubstituted pyridine ring and achieved the first total synthesis of this molecule on a gram scale. A bicyclic intermediate was expeditiously prepared by using [2 + 2] photocycloaddition and chemoselective Baeyer−Villiger oxidation, which was further elaborated to a densely substituted aza‐triene. An electrocyclization−aromatization cascade was exploited to forge the tetracyclic core of the natural product, and the side chain was introduced through diastereoselective acylation and reduction.
• Welwistatin Support Studies:  Expansion and Limitation of Aryllead(IV) Coupling Reactions
  作者：Jibo Xia、Lauren E. Brown、Joseph P. Konopelski

  DOI：10.1021/jo071156l

  日期：2007.8.31

  target step involves lead-mediated arylation of sterically demanding aryl groups and carbon acid coupling partners in order to establish the highly congested tetracyclic core structure. Type 7 β-ketoesters and β-ketonitriles were successfully arylated with a variety of ortho- and meta-substituted aryllead compounds generated by a halogen−boron−lead exchange sequence. The enolates of compounds 15, 19

  描述了有关welwistatin系统总合成的最新支持研究。目标步骤涉及空间需要的芳基和碳酸偶联剂的铅介导的芳基化，以建立高度拥挤的四环核结构。键入7 β酮酯和β酮腈成功芳基化与各种被卤素-硼-铅交换序列生成邻位和间位取代的芳基铅化合物。化合物的烯醇化物15，19，和25，邻近该芳基化位点，每个轴承的全碳季中心，未能耦合。