4-[dimethyl(phenyl)silyl]-5-methyloxolan-2-one | 1397692-64-6

• 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: 4-[dimethyl(phenyl)silyl]-5-methyloxolan-2-one
• CAS: 1397692-64-6
• 化学式: C₁₃H₁₈O₂Si
• 分子量: 234.37
• InChiKey: XHQYSNJFRRKILO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.31
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-[dimethyl(phenyl)silyl]-5-methyloxolan-2-one 在 过氧乙酸 、 sodium acetate 、 溶剂黄146 、 potassium bromide 作用下， 反应 16.0h， 生成 3-hydroxy-4-pentanolide of (3S,4R)-3,4-dihydroxypentanoic acid 、 (-)-(4R,5S)-dihydro-4-hydroxy-5-methyl-2(3H)-furanone
  参考文献：
  名称：

  Total Syntheses of (−)-Grandinolide and (−)-Sapranthin by the Sharpless Asymmetric Dihydroxylation of Methyltrans-3-Pentenoate: Elucidation of the Stereostructure of (−)-Sapranthin

  摘要：

  Methyl trans-3-pentenoate (7) was converted into the cis-substituted gamma-lactone 8 in a single step with 78 % ee. The derived enolate dilithio-8 was alkylated trans-selectively with primary iodoalkanes. with 1-iodobutane dilithio-8 afforded, after esterification with isovaleroyl chloride, the epi-blast mycinone 9, Dilithio-8 gave (-)-grandinolide (11) with 1-iodo-19-phenylnonadecane (20), A third trans-selective alkylation of dilithio-8 was undertaken with 16-iodo-1.5-hexadecadiene-7,9-diyne (21). This gave the gamma-lactone 12. which had the published relative configuration of (-)-sapranthin but different spectroscopic data, When the OH group of lactone 8 was inverted (to hydroxylactone 40) and the derived enolate dilithio-40 alkylated with iodide 21, lactone 41 resulted, Its H-1 and C-13 NMR spectra and the sign and value of optical rotation coincide with the data of natural sapranthin, These findings establish that (-)-sapranthin possesses the relative and absolute configuration of stereoformula 41. The synthesis of iodide 21 was performed via the dienoic carboxylic ester trans-23 which stemmed from the Claisen-Ireland rearrangement (27 --> 28/29)/esterification (28/29 --> 26)/Cope rearrangement (26 - 23) sequence shown in Scheme 5.

  DOI：

  10.1002/(sici)1521-3765(19981102)4:11<2342::aid-chem2342>3.0.co;2-q
• 作为产物：
  描述：

  5-甲基-2(5H)-呋喃酮 、 苯基二甲基氯硅烷 在 lithium 、 copper(l) cyanide 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以80%的产率得到4-[dimethyl(phenyl)silyl]-5-methyloxolan-2-one
  参考文献：
  名称：

  有机合成中的碲：丁烯醇和丁醇化物的通用方法

  摘要：

  使用羟基-乙烯基碲化物以高对映体纯度制备了天然存在的丁醇化物（-）-blastmycinactactol，（+）-blastmycinone，（-）-NFX-2，（+）-anticincinone以及丁烯内酯Acaterin的四种立体异构体。作为起始原料。

  DOI：

  10.1016/j.tet.2012.09.074

文献信息

• Tellurium in organic synthesis: a general approach to buteno- and butanolides
  作者：Renan S. Ferrarini、Alcindo A. Dos Santos、João V. Comasseto

  DOI：10.1016/j.tet.2012.07.088

  日期：2012.10

  The naturally occurring butanolides (−)-blastmycinolactol, (+)-blastmycinone, (−)-NFX-2, (+)-antimycinone as well as the four stereoisomers of the butenolide Acaterin were prepared in high enantiomeric purity using hydroxy-vinyl tellurides as starting materials.

  使用羟基-乙烯基碲化物以高对映体纯度制备了天然存在的丁醇化物（-）-blastmycinactactol，（+）-blastmycinone，（-）-NFX-2，（+）-anticincinone以及丁烯内酯Acaterin的四种立体异构体。作为起始原料。