3-<(Triisopropylsilyl)oxy>cyclohexene | 143545-97-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-<(Triisopropylsilyl)oxy>cyclohexene
• 英文别名: (2-cyclohexen-1-yloxy)triisopropylsilane；Cyclohex-2-en-1-yloxy-tri(propan-2-yl)silane
• CAS: 143545-97-5
• 化学式: C₁₅H₃₀OSi
• 分子量: 254.488
• InChiKey: SQSOYNZZNMTGPV-UHFFFAOYSA-N

物化性质

• 沸点：
  276.4±29.0 °C(Predicted)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.29
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.87
• 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：

  3-<(Triisopropylsilyl)oxy>cyclohexene 在 氧气 、 臭氧 、 dibenzylammonium trifluoroacetate 、 三甲氧基磷 作用下， 以 四氢呋喃 为溶剂， 生成 (+/-)-3-<(Triisopropylsilyl)oxy>cyclopent-1-ene-1-carboxaldehyde
  参考文献：
  名称：

  An allylic azide route to 4'-azido carbocyclic nucleosides. Synthesis of (.+-.)-(1'.alpha.,2'.alpha.,3'.beta.)- and (.+-.)-(1'.alpha.,2'.beta.,3'.beta.)-1-[1-azido-2-hydroxy-1-(hydroxymethyl)-3-cyclopentyl]thymine

  摘要：

  Treatment of (+/-)-1-[[(tert-butyldiphenylsilyl)oxy]methyl]-3-methoxycyclopent-1-ene (17) with azidotrimethylsilane under Lewis acid catalyzed conditions gave an equilibrium mixture of allylic azides 18 and 19. Epoxidation of this mixture with peroxybenzimidic acid gave key epoxide (+/-)-(1alpha,2alpha,5alpha)-2-azido-2-[[tert-butyldiphenylsilyl)oxy]methyl]-6-oxabicyclo[3.1.0]hexane (5). Alternate routes designed to give tertiary azide precursors to 5 led to unanticipated products which are described. Title compound 28 was prepared by ring opening of 5 under Vorbruggen conditions followed by deprotection. Inversion of configuration at C-6' to give compound 30 was effected via O2,6'-cyclic intermediates 31 and 32. The relative stereochemistry of compounds in this series was suggested by NOE data for bromohydrins 23 and 26 and was confirmed by preparation of the fused oxetane 34.

  DOI：

  10.1021/jo00048a010
• 作为产物：
  描述：

  三异丙基氯硅烷 、 2-环己烯醇 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到3-<(Triisopropylsilyl)oxy>cyclohexene
  参考文献：
  名称：

  An allylic azide route to 4'-azido carbocyclic nucleosides. Synthesis of (.+-.)-(1'.alpha.,2'.alpha.,3'.beta.)- and (.+-.)-(1'.alpha.,2'.beta.,3'.beta.)-1-[1-azido-2-hydroxy-1-(hydroxymethyl)-3-cyclopentyl]thymine

  摘要：

  Treatment of (+/-)-1-[[(tert-butyldiphenylsilyl)oxy]methyl]-3-methoxycyclopent-1-ene (17) with azidotrimethylsilane under Lewis acid catalyzed conditions gave an equilibrium mixture of allylic azides 18 and 19. Epoxidation of this mixture with peroxybenzimidic acid gave key epoxide (+/-)-(1alpha,2alpha,5alpha)-2-azido-2-[[tert-butyldiphenylsilyl)oxy]methyl]-6-oxabicyclo[3.1.0]hexane (5). Alternate routes designed to give tertiary azide precursors to 5 led to unanticipated products which are described. Title compound 28 was prepared by ring opening of 5 under Vorbruggen conditions followed by deprotection. Inversion of configuration at C-6' to give compound 30 was effected via O2,6'-cyclic intermediates 31 and 32. The relative stereochemistry of compounds in this series was suggested by NOE data for bromohydrins 23 and 26 and was confirmed by preparation of the fused oxetane 34.

  DOI：

  10.1021/jo00048a010

文献信息

• Carbon-Nitrogen Bond Formation between Allyl Silyl Ether and Hydrazide Promoted by Mercuric Triflate Catalyst
  作者：Hirofumi Yamamoto、Naoto Yamasaki、Shingo Yoshidome、Ikuo Sasaki、Kosuke Namba、Hiroshi Imagawa、Mugio Nishizawa

  DOI：10.1055/s-0031-1290758

  日期：2012.4

  An efficient method for carbon–nitrogen bond formation between ally silyl ethers and N , N -acyltosylhydrazine was developed under very mild conditions using 2 mol% of mercuric triflate [Hg(OTf) 2 ] as a catalyst. This method does not require the use of any ligand system or supplementary additives and is applicable to the preparation of various N -allylhydrazides with good to excellent yields.

  使用 2 mol% 的三氟甲磺酸汞 [Hg(OTf) 2 ] 作为催化剂，在非常温和的条件下开发了一种在烯丙基甲硅烷基醚和 N , N - 酰基甲苯基肼之间形成碳 - 氮键的有效方法。该方法不需要使用任何配体系统或辅助添加剂，适用于制备各种N-烯丙基酰肼，收率良好。
• An allylic azide route to 4'-azido carbocyclic nucleosides. Synthesis of (.+-.)-(1'.alpha.,2'.alpha.,3'.beta.)- and (.+-.)-(1'.alpha.,2'.beta.,3'.beta.)-1-[1-azido-2-hydroxy-1-(hydroxymethyl)-3-cyclopentyl]thymine
  作者：Hans Maag、Robert M. Rydzewski

  DOI：10.1021/jo00048a010

  日期：1992.10

  Treatment of (+/-)-1-[[(tert-butyldiphenylsilyl)oxy]methyl]-3-methoxycyclopent-1-ene (17) with azidotrimethylsilane under Lewis acid catalyzed conditions gave an equilibrium mixture of allylic azides 18 and 19. Epoxidation of this mixture with peroxybenzimidic acid gave key epoxide (+/-)-(1alpha,2alpha,5alpha)-2-azido-2-[[tert-butyldiphenylsilyl)oxy]methyl]-6-oxabicyclo[3.1.0]hexane (5). Alternate routes designed to give tertiary azide precursors to 5 led to unanticipated products which are described. Title compound 28 was prepared by ring opening of 5 under Vorbruggen conditions followed by deprotection. Inversion of configuration at C-6' to give compound 30 was effected via O2,6'-cyclic intermediates 31 and 32. The relative stereochemistry of compounds in this series was suggested by NOE data for bromohydrins 23 and 26 and was confirmed by preparation of the fused oxetane 34.