(5S,6S)-6-(2-(tert-butyldimethylsilyloxy)ethyl)-5-methyltetrahydro-2H-pyran-2-yl acetate | 756834-74-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (5S,6S)-6-(2-(tert-butyldimethylsilyloxy)ethyl)-5-methyltetrahydro-2H-pyran-2-yl acetate
• 英文别名: [(5S,6S)-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-5-methyloxan-2-yl] acetate
• CAS: 756834-74-9
• 化学式: C₁₆H₃₂O₄Si
• 分子量: 316.513
• InChiKey: OQRZPHXXGDHQCT-XRJCJLGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (5S,6S)-6-(2-(tert-butyldimethylsilyloxy)ethyl)-5-methyltetrahydro-2H-pyran-2-yl acetate 在 氢氟酸 、 zinc(II) chloride 作用下， 以 乙醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 1.67h， 生成 (E)-1-((2R,5S,6S)-6-(2-hydroxyethyl)-5-methyltetrahydro-2H-pyran-2-yl)pent-3-en-2-one
  参考文献：
  名称：

  Synthesis of Bistramide A

  摘要：

  We have developed an efficient and highly stereocontrolled synthesis of bistramide A, a selective activator of protein kinase C isotype delta. Our synthetic strategy featured a novel bidirectional approach for spiroketal construction based on the ring-opening/cross-metathesis sequence employing a highly strained cyclopropenone acetal. The synthesis afforded the final target with the longest linear sequence of 15 steps and provided unambiguous structural determination of bistramide A, including assignment of the previously unknown C(37) stereochemistry.

  DOI：

  10.1021/ja046588h
• 作为产物：
  描述：

  (5S,6S)-6-[2-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-5-methyl-5,6-dihydro-pyran-2-one 在 palladium on activated charcoal 吡啶 、 4-二甲氨基吡啶 、 氢气 、 二异丁基氢化铝 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 6.67h， 生成 (5S,6S)-6-(2-(tert-butyldimethylsilyloxy)ethyl)-5-methyltetrahydro-2H-pyran-2-yl acetate
  参考文献：
  名称：

  Synthesis of Bistramide A

  摘要：

  We have developed an efficient and highly stereocontrolled synthesis of bistramide A, a selective activator of protein kinase C isotype delta. Our synthetic strategy featured a novel bidirectional approach for spiroketal construction based on the ring-opening/cross-metathesis sequence employing a highly strained cyclopropenone acetal. The synthesis afforded the final target with the longest linear sequence of 15 steps and provided unambiguous structural determination of bistramide A, including assignment of the previously unknown C(37) stereochemistry.

  DOI：

  10.1021/ja046588h

文献信息

• Stereoselective Total Synthesis of Bistramide A
  作者：J. S. Yadav、Lakshindra Chetia

  DOI：10.1021/ol702095n

  日期：2007.10.1

  A highly stereoselective and convergent total synthesis of bistramide A is described. The salient feature of this synthesis is the construction of the spiroketal subunit by hydrolysis of dialkylated tosylmethyl isocyanide derivative derived via alkylation of TosMIC with suitably substituted halohydrin derivatives.

  描述了双立体酰胺A的高度立体选择性和收敛的全合成。该合成的显着特征是通过将TosMIC与合适取代的卤代醇衍生物进行烷基化而衍生的二烷基化的甲苯磺酰基甲基异氰化物衍生物的水解来构建螺环亚基。
• Spiroacetal Formation through Telescoped Cycloaddition and Carbon-Hydrogen Bond Functionalization: Total Synthesis of Bistramide A
  作者：Xun Han、Paul E. Floreancig

  DOI：10.1002/anie.201406819

  日期：2014.10.6

  Spiroacetals can be formed through a one‐pot sequence of a hetero‐Diels–Alder reaction, an oxidative carbon–hydrogen bond cleavage, and an acid treatment. This convergent approach expedites access to a complex molecular subunit which is present in numerous biologically active structures. The utility of the protocol is demonstrated through its application to a brief synthesis of the actin‐binding cytotoxin

  螺缩醛可以通过杂狄尔斯-阿尔德反应、氧化碳氢键断裂和酸处理的一锅顺序形成。这种趋同方法加快了对存在于众多生物活性结构中的复杂分子亚基的访问。该协议的实用性通过其在肌动蛋白结合细胞毒素双酰胺 A 的简要合成中的应用得到证明。