dihydro-5-(tert-butyldiphenylsiloxymethyl)-4-methyl-2(3H)-furanone | 103233-14-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: dihydro-5-(tert-butyldiphenylsiloxymethyl)-4-methyl-2(3H)-furanone
• 英文别名: (4S,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-4-methyloxolan-2-one
• CAS: 103233-14-3；106820-50-2；110098-09-4；140710-23-2；140710-24-3
• 化学式: C₂₂H₂₈O₃Si
• 分子量: 368.548
• InChiKey: IPFNDQXHBBRQSL-PXNSSMCTSA-N

物化性质

• 沸点：
  455.1±27.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  dihydro-5-(tert-butyldiphenylsiloxymethyl)-4-methyl-2(3H)-furanone 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以59%的产率得到(4S,5R)-dihydro-5-hydroxymethyl-4-methyl-2(3H)-furanone
  参考文献：
  名称：

  Regio-, stereo-, and enantioselective synthesis of cyclobutanols by means of the photoaddition of 1,3-dioxin-4-ones and lipase-catalyzed acetylation

  摘要：

  Homochiral cis-2-hydroxymethylcyclobutanols, their all cis 3-methyl, and 4-hydroxymethyl derivatives were synthesized from 1,3-dioxin-4-ones via cyclobutane ring formation by [2+2]photocycloaddition, dioxanone ring cleavage, and reduction, followed by lipase-catalyzed kinetic resolution of the resulted cyclobutanols. The chiral cyclobutanols thus obtained have been converted to the corresponding gamma-lactones which are potential precursors for a series of biologically active compounds.

  DOI：

  10.1016/s0957-4166(00)80211-6
• 作为产物：
  描述：

  (1S^*,2S^*,3R^*)-2-(tert-butyldiphenylsiloxymethyl)-3-methylcyclobutanol 在 disodium hydrogenphosphate 、 4 A molecular sieve 、 间氯过氧苯甲酸 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 17.0h， 生成 dihydro-5-(tert-butyldiphenylsiloxymethyl)-4-methyl-2(3H)-furanone
  参考文献：
  名称：

  Regio-, stereo-, and enantioselective synthesis of cyclobutanols by means of the photoaddition of 1,3-dioxin-4-ones and lipase-catalyzed acetylation

  摘要：

  Homochiral cis-2-hydroxymethylcyclobutanols, their all cis 3-methyl, and 4-hydroxymethyl derivatives were synthesized from 1,3-dioxin-4-ones via cyclobutane ring formation by [2+2]photocycloaddition, dioxanone ring cleavage, and reduction, followed by lipase-catalyzed kinetic resolution of the resulted cyclobutanols. The chiral cyclobutanols thus obtained have been converted to the corresponding gamma-lactones which are potential precursors for a series of biologically active compounds.

  DOI：

  10.1016/s0957-4166(00)80211-6

文献信息

• Studies of Acyl Nitrene Insertions. A Stereocontrolled Route toward Lankacidin Antibiotics
  作者：David R. Williams、Christian M. Rojas、Stéphane L. Bogen

  DOI：10.1021/jo981310r

  日期：1999.2.1

  Photochemically generated acyl nitrenes undergo facile addition to 4,5-dihydrofurans 20 and 24b to yield the novel 2-ethoxyoxazolines 21 and 25. The regiocontrolled C=C insertion has provided for introduction of the sterically hindered C-3 amido appendage of the lankacidins 1-4 with high stereoselectivity. High chemoselectivity for the C=C insertion pathway was demonstrated upon production of the acyl

  光化学生成的酰基腈易于加入4,5-二氢呋喃20和24b中，以生成新型的2-乙氧基恶唑啉21和25。区域控制的C = C插入为引入Lankacidins 1的空间位阻C-3酰胺基提供了便利。 -4具有高立体选择性。由叠氮化物33b产生酰基腈中间体时，证明了对C ＝ C插入途径的高化学选择性。烯丙基C（3）-H插入与C = C添加的分子内竞争产生了七元N-酰基氮丙啶34a，b的排他形成。恶唑啉的潜在醛官能团（如21和25）在短暂水解后就暴露出来，可以进行进一步的化学修饰。来自25的内酯的Wittig缩合导致内酯片段5的合成 包含所有必需的立体化学和功能，可将其整合到兰卡酸抗生素中。酰基氮烯插入4,5-二氢呋喃提供了一条通往异常β-酰胺酸和氨基糖衍生物的途径，这是通过立体控制酰胺基呋喃糖衍生物31和32的形成而显示的。酰基腈的三步添加过程包括： 2,5-二烷氧基恶唑啉中间体和Wittig碳链延长提供了新型β-酰胺基酯的立体控制形成。