citronellol t-butyldiphenylsilyl ether | 131883-94-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: citronellol t-butyldiphenylsilyl ether
• 英文别名: tert-butyl((3,7-dimethyloct-6-en-1-yl)oxy)diphenylsilane；Tert-butyl-(3,7-dimethyloct-6-enoxy)-diphenylsilane
• CAS: 131883-94-8
• 化学式: C₂₆H₃₈OSi
• 分子量: 394.673
• InChiKey: ARPGYJBHYQRQNW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.34
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  citronellol t-butyldiphenylsilyl ether 在 lithium aluminium tetrahydride 、 二甲基硫 、 臭氧 作用下， 以 乙醚 为溶剂， 反应 16.2h， 生成 (+/-)-1-<(tert-Butyldiphenylsilyl)oxy>-6-hydroxy-3-methylhexane
  参考文献：
  名称：

  Intramolecular formal [3 + 2] cycloaddition of alkenes and benzylic cations. Stereoselective synthesis of 1,2,3,4,4a,9a-hexahydrofluorenes

  摘要：

  The Lewis acid-promoted intramolecular formal [3 + 2]-atom 'cycloaddition' of alkenes with benzylic cations derived from benzylic alcohols and quinone methides affords products in good yield and with remarkable stereoselectivity. Benzylic alcohol 20 affords hexahydrofluorene 36 with three new stereogenic centers in 73% yield as a 10:1 mixture of diastereomers. The scope and limitations of these reactions were explored by varying the substitution pattern on the benzylic cation, the cyclization initiators, and the alkene terminators.

  DOI：

  10.1021/jo00071a024
• 作为产物：
  描述：

  香茅醇 、 叔丁基二苯基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 以89%的产率得到citronellol t-butyldiphenylsilyl ether
  参考文献：
  名称：

  催化、逆热力学位置烯烃异构化

  摘要：

  C=C双键的位置异构化是烯烃区域异构体相互转化的有力策略。然而，现有方法提供了从不太稳定的起始材料获得热力学上更稳定的异构体的途径。在这里，我们报告了在光化学辐照下促进逆热力学位置烯烃异构化的双催化剂系统的发现，提供了直接从共轭的内部烯烃起始材料获得末端烯烃异构体的途径。该方法的实用性在多种富电子/贫电子烯烃的去共轭中以及通过对天然产物合成的战略应用得到证明。机理研究与区域特异性双分子均裂取代（S H2') 机制通过烯丙基钴肟中间体进行。

  DOI：

  10.1021/jacs.1c12043

文献信息

• New Metal-Free One-Pot Synthesis of Substituted Allenes from Enones
  作者：Meng Tang、Chun-An Fan、Fu-Min Zhang、Yong-Qiang Tu、Wen-Xue Zhang、Ai-Xia Wang

  DOI：10.1021/ol802445p

  日期：2008.12.18

  A new metal-free, one-pot synthesis of substituted allenes from enones was discovered for the first time, in which a tertiary amine as a base was found to be an effective promoter in such novel transformations. The present synthetic protocol proceeded readily with high compatibility of sensitive functional groups, and it provides a new efficient way to access a series of synthetically important allenes

  首次发现了一种新的无金属，一锅法从烯酮合成取代的丙二烯的方法，其中发现叔胺为碱是这种新型转化的有效促进剂。本合成方案易于进行，且与敏感官能团具有高度相容性，并且它提供了一种无需使用金属试剂或催化剂即可获得一系列合成上重要的烯的有效途径。
• The conversion of olefins to β-keto esters: Ozonolysis of olefins followed by in situ reduction with tin(II) chloride in the presence of ethyl diazoacetate.
  作者：Christopher R. Holmquist、Eric J. Roskamp

  DOI：10.1016/s0040-4039(00)97786-4

  日期：1990.1

  β-keto esters by treatment with ozone followed by the addition of tin(H) chloride and ethyl diazoacetate. Monosubstituted olefins are first treated with ozone in the presence of methanol to generate methoxy hydroperoxides. The hydroperoxides are subsequently reduced with tin(II) chloride in the presence of ethyl diazoacetate to produce β-keto esters.

  通过用臭氧处理，然后添加氯化锡（H）和重氮乙酸乙酯，将三取代的烯烃转化为β-酮酸酯。首先在甲醇存在下用臭氧处理单取代的烯烃，以生成甲氧基氢过氧化物。氢过氧化物随后在重氮乙酸乙酯存在下用氯化锡（II）还原，生成β-酮酸酯。
• Lewis acid-promoted selective rearrangement of trisubstituted epoxides to aldehydes or ketones
  作者：Keiji Maruoka、Noriaki Murase、Ronan Bureau、Takashi Ooi、Hisashi Yamamoto

  DOI：10.1016/s0040-4020(01)90389-8

  日期：1994.3

  Rearrangement of trisubstituted epoxides has been effected under the influence of various Lewis acids. Among these, methylaluminum bis(4-bromo-2,6-di-tert-butylphenoxide) (MABR) can be selectively rearranged from trisubstituted epoxides to aldehydes, while antimony pentafluoride is employable for selective rearrangement to ketones under mild conditions.
• Precipiton Reagents:  Precipiton Phosphines for Solution-Phase Reductions
  作者：Todd Bosanac、Craig S. Wilcox

  DOI：10.1021/ol049369+

  日期：2004.7.1

  Several Precipiton phosphines were prepared and employed in the Staudinger reaction and in the reduction of secondary ozonides. Both amines and aldehdyes were obtained in good to excellent yields and purities. After use of the phosphine, isomerization and precipitation of the spent phosphorus reagent were induced by exposure to visible light in the presence of erythrosin B, a triplet sensitizer. Products were isolated by simple filtration. The use of the triplet sensitizer has the added advantage of eliminating [2 + 2] cycloaddition reactions between trans-Precipitons.
• HOLMQUIST, CHRISTOPHER R.;ROSKAMP, ERIC J., TETRAHEDRON LETT., 31,(1990) N5, C. 4991-4994
  作者：HOLMQUIST, CHRISTOPHER R.、ROSKAMP, ERIC J.

  DOI：——

  日期：——