Trimethyl(3-trityloxyprop-1-ynyl)silane | 144242-25-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: Trimethyl(3-trityloxyprop-1-ynyl)silane
• CAS: 144242-25-1
• 化学式: C₂₅H₂₆OSi
• 分子量: 370.566
• InChiKey: DVMHKXFHCHNUFK-UHFFFAOYSA-N

物化性质

• 沸点：
  442.3±40.0 °C(Predicted)
• 密度：
  1.037±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.88
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Trimethyl(3-trityloxyprop-1-ynyl)silane 在 甲醇 、 六甲基磷酰三胺 、 sodium hydroxide 、 正丁基锂 、 甲基锂 、 十六烷基三甲基溴化铵 、 二异丁基氢化铝 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 45.5h， 生成 ((1S,2S,3R)-2-Bromo-2,3-dimethyl-3-trimethylsilanyl-cyclopropyl)-methanol
  参考文献：
  名称：

  Towards Synthesis of Calysterols, Marine Sterols with Cyclopropene Moiety in the Side Chain: Synthesis of 26,27-Dinor-23H-isocalysterol

  摘要：

  26,27-Dinor-23H-isocalysterol 24已经从乙酸乙酯6β-甲氧基-3α,5-环-5α-孕酮-21-酸酯（18）中合成，收率为19％（6步）。为了构建侧链，使用1-溴-1,2-二甲基-c-3-碘甲基-c-2-（三甲基硅基）环丙烷16的乙酸锂盐烷基化乙酸酯18。已经证明，21位酯基还原和3,5-环甾体系统重排与侧链功能相兼容。发现1,1-二溴-2-（三甲基硅基）环丙烷的甲基化伴随着涉及三甲基硅基团1,2-迁移的重排。

  DOI：

  10.1135/cccc19981575
• 作为产物：
  描述：

  三甲基氯硅烷 、 1-trityloxy-2-propyne 在 正丁基锂 作用下， 生成 Trimethyl(3-trityloxyprop-1-ynyl)silane
  参考文献：
  名称：

  Synthesis of four stereoisomeric tetrose derivatives from propargyl alcohol. One-carbon homologation of vinylsilanes via .alpha.,.beta.-epoxy silanes

  摘要：

  Silicon-mediated synthesis of stereoisomeric tetroses 1, 2, 3, and 4, from propargyl alcohol, is described. An allylic alcohol bearing the trimethylsilyl group in the gamma-position, rac-9b, was subjected to the Sharpless kinetic resolution to give (2S)-9b and the (2S,3S,4S)-epoxide 10a of very high enantiomeric purity (greater-than-or-equal-to 97% ee). Compound (2S)-9b was epoxidized with tert-butyl hydroperoxide and vanadyl acetylacetonate to give epoxide 14a as the major product. Epoxy silanes 10a and 14a were treated with benzenethiol in the presence of silica gel to give the corresponding sulfides (11a and 16a). Sulfides 11b and 16b were oxidized to sulfoxides which, without isolation, were subjected to the Pummerer rearrangement followed by hydrolysis. Intermediate vinylsilane 9a was prepared from vinylsilane 6 via epoxy silane 7 using a novel homologation method.

  DOI：

  10.1021/jo00050a041

文献信息

• Synthesis of four stereoisomeric tetrose derivatives from propargyl alcohol. One-carbon homologation of vinylsilanes via .alpha.,.beta.-epoxy silanes
  作者：Barbara Achmatowicz、Piotr Raubo、Jerzy Wicha

  DOI：10.1021/jo00050a041

  日期：1992.11

  Silicon-mediated synthesis of stereoisomeric tetroses 1, 2, 3, and 4, from propargyl alcohol, is described. An allylic alcohol bearing the trimethylsilyl group in the gamma-position, rac-9b, was subjected to the Sharpless kinetic resolution to give (2S)-9b and the (2S,3S,4S)-epoxide 10a of very high enantiomeric purity (greater-than-or-equal-to 97% ee). Compound (2S)-9b was epoxidized with tert-butyl hydroperoxide and vanadyl acetylacetonate to give epoxide 14a as the major product. Epoxy silanes 10a and 14a were treated with benzenethiol in the presence of silica gel to give the corresponding sulfides (11a and 16a). Sulfides 11b and 16b were oxidized to sulfoxides which, without isolation, were subjected to the Pummerer rearrangement followed by hydrolysis. Intermediate vinylsilane 9a was prepared from vinylsilane 6 via epoxy silane 7 using a novel homologation method.
• Towards Synthesis of Calysterols, Marine Sterols with Cyclopropene Moiety in the Side Chain: Synthesis of 26,27-Dinor-23H-isocalysterol
  作者：Alicja Kurek-Tyrlik、Kazimierz Minksztym、Jerzy Wicha

  DOI：10.1135/cccc19981575

  日期：——

  26,27-Dinor-23H-isocalysterol 24 has been synthesized in 19% yield (6 steps) from ethyl 6β-methoxy-3α,5-cyclo-5α-pregnan-21-oate (18). For construction of the side chain, alkylation of lithium salt of ester 18 with 1-bromo-1,2-dimethyl-c-3-iodomethyl-c-2-(trimethylsilyl)cyclopropane 16 was used. It has been shown that reduction of the ester group in position 21 and rearrangement of the 3,5-cyclosteroid system are compatible with the sidechain functionalities. It has been found that methylation of 1,1-dibromo-2-(trimethylsilyl)cyclopropane is accompanied by an rearrangement involving 1,2-migration of the trimethylsilyl group.

  26,27-Dinor-23H-isocalysterol 24已经从乙酸乙酯6β-甲氧基-3α,5-环-5α-孕酮-21-酸酯（18）中合成，收率为19％（6步）。为了构建侧链，使用1-溴-1,2-二甲基-c-3-碘甲基-c-2-（三甲基硅基）环丙烷16的乙酸锂盐烷基化乙酸酯18。已经证明，21位酯基还原和3,5-环甾体系统重排与侧链功能相兼容。发现1,1-二溴-2-（三甲基硅基）环丙烷的甲基化伴随着涉及三甲基硅基团1,2-迁移的重排。