4-(tert-butyldimethylsilyloxy)-2-methylbutanal | 115797-15-4

• 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: 4-(tert-butyldimethylsilyloxy)-2-methylbutanal
• 英文别名: 2-methyl-4-[(tert-butyldimethylsilyl)oxy]butanal；4-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]-2-methylbutanal；4-[tert-butyl(dimethyl)silyl]oxy-2-methylbutanal
• CAS: 115797-15-4
• 化学式: C₁₁H₂₄O₂Si
• 分子量: 216.396
• InChiKey: QQTVXUATCMPMSL-UHFFFAOYSA-N

物化性质

• 沸点：
  240.3±23.0 °C(Predicted)
• 密度：
  0.865±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(tert-butyldimethylsilyloxy)-2-methylbutanal 在 sodium tetrahydroborate 作用下， 生成 4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol
  参考文献：
  名称：

  Enantioselective Hydroformylation of 1-Alkenes with Commercial Ph-BPE Ligand

  摘要：

  A rhodium complex, in conjunction with commercially available Ph-BPE ligand, catalyzes the branch-selective asymmetric hydroformylation of 1-alkenes and rapidly generates alpha-chiral aldehydes. A wide range of terminal olefins Including 1-dodecene were examined, and all delivered high enantioselectivity (up to 98:2 er) as well as good branch:linear ratios (up to 15:1).

  DOI：

  10.1021/acs.orglett.5b01421
• 作为产物：
  描述：

  4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 生成 4-(tert-butyldimethylsilyloxy)-2-methylbutanal
  参考文献：
  名称：

  Relative Asymmetric Induction in the Intramolecular Reaction between Alkynes and Cyclopropylcarbene−Chromium Complexes:  Stereocontrolled Synthesis of Five-Membered Rings Fused to Oxygen Heterocycles

  摘要：

  Synthesis of cyclopentenone derivatives fused to oxygen heterocycles by means of the intramolecular coupling of alkynes and cyclopropylcarbene-chromium complexes has been examined for a variety of cases in which the tethering chain features a stereogenic center. In some cases, this process proceeds with a very high degree of stereoselectivity; however, the extent and direction of relative asymmetric induction is very dependent upon the position of the chiral atom within the tethering chain and the length of the tethering chain. In the best case, featuring a two-carbon tether and a stereogenic center at the homopropargylic position (complex 1N), the heterocyclic ring was produced with 97:3 selectivity for the cis heterocycle (3N). In the worst case, featuring a three-carbon tether and a stereogenic center at the homopropargylic position (complexes 1F and ii), no stereoselectivity was observed. Improvement in stereoselectivity was noticed when terminal alkynes were replaced by silylated alkynes and when proton sources were eliminated from the reaction.

  DOI：

  10.1021/jo982144q

文献信息

• Palladium Hydroxide Catalyzed Isomerization of Primary Allylic Alcohols to Aldehydes: Application to the Formal Synthesis of (−)-Brevisamide
  作者：Gowravaram Sabitha、Sambit Nayak、M. Bhikshapathi、J. S. Yadav

  DOI：10.1021/ol102658d

  日期：2011.2.4

  The Pd-catalyzed isomerization of primary allylic alcohols into the corresponding saturated aldehydes has been achieved at room temperature for the first time in good to excellent yields under mild conditions. The functional group compatibility in this reaction is studied, and this new methodology has been successfully applied in the synthesis of a C5-C13 tetrahydropyran ring system of (-)-brevisamide in seven steps.
• Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene−Chromium Complexes:  A Formal Total Synthesis of (±)-Vitamin D₃
  作者：Jingbo Yan、James W. Herndon

  DOI：10.1021/jo972186z

  日期：1998.4.1

  The intramolecular coupling of alkynes and cyclopropylcarbene-chromium complexes has been examined. Complexes that feature a stereogenic center at the propargylic position of the alkyne-carbene tether are the focus of this paper. The reaction produces a cyclopentadienone intermediate fused to an oxygen heterocycle, which is reduced to the corresponding cyclopentenone under the reaction conditions (100 degrees C in aqueous toluene). The preexisting stereogenic center has a powerful influence on the reduction of the cyclopentadienone ring, and predominantly a single diastereomer is produced in the reaction. Reductive cleavage of the heterocyclic ring with retention of stereochemistry affords compounds featuring a stereocenter on the five-membered ring and on a side chain. Use of the above reaction processes for the synthesis of the vitamin D precursor de-ABC-cholestan-14-one is also discussed.
• The necessity of an intact polyene for the biological isomerization of vitamin A
  作者：Wing C. Law、Robert R. Rando、Stefano. Canonica、Fadila. Derguini、Koji. Nakanishi

  DOI：10.1021/ja00225a062

  日期：1988.8
• LAW, WING C.;RANDO, ROBERT R.;CANONICA, STEFANO;DERGUINI, FADILA;NAKANISH+, J. AMER. CHEM. SOC., 110,(1988) N 17, C. 5915-5917
  作者：LAW, WING C.、RANDO, ROBERT R.、CANONICA, STEFANO、DERGUINI, FADILA、NAKANISH+

  DOI：——

  日期：——
• Enantioselective Hydroformylation of 1-Alkenes with Commercial Ph-BPE Ligand
  作者：Zhiyong Yu、Meredith S. Eno、Alexandra H. Annis、James P. Morken

  DOI：10.1021/acs.orglett.5b01421

  日期：2015.7.2

  A rhodium complex, in conjunction with commercially available Ph-BPE ligand, catalyzes the branch-selective asymmetric hydroformylation of 1-alkenes and rapidly generates alpha-chiral aldehydes. A wide range of terminal olefins Including 1-dodecene were examined, and all delivered high enantioselectivity (up to 98:2 er) as well as good branch:linear ratios (up to 15:1).