4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol | 190016-52-5

• 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: 4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol
• 英文别名: 4-(tert-butyldimethylsilyloxy)-2-methyl-butan-1-ol；4-{[tert-Butyl(dimethyl)silyl]oxy}-2-methylbutan-1-ol；4-[tert-butyl(dimethyl)silyl]oxy-2-methylbutan-1-ol
• CAS: 190016-52-5
• 化学式: C₁₁H₂₆O₂Si
• 分子量: 218.412
• InChiKey: LWSKSGVHPMJOKM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol 在 palladium on activated charcoal 正丁基锂 、 草酰氯 、 三氟化硼乙醚 、 氢气 、 二甲基亚砜 、 三苯基膦 作用下， 以 乙醇 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 12.0h， 生成 (2R,3R)-4-hydroxy-3-[(2R)-4-hydroxybutan-2-yl]-2-methylcyclopentan-1-one
  参考文献：
  名称：

  Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene−Chromium Complexes:  A Formal Total Synthesis of (±)-Vitamin D₃

  摘要：

  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.

  DOI：

  10.1021/jo972186z
• 作为产物：
  描述：

  3-甲基-3-丁烯-1-醇 在 sodium hydroxide 、 硼烷四氢呋喃络合物 、 双氧水 作用下， 生成 4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol
  参考文献：
  名称：

  Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene−Chromium Complexes:  A Formal Total Synthesis of (±)-Vitamin D₃

  摘要：

  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.

  DOI：

  10.1021/jo972186z

文献信息

• Sustainable radical reduction through catalyzed hydrogen atom transfer reactions (CHAT-reactions)
  作者：Andreas Gansäuer、Matthias Otte、Frederik Piestert、Chun-An Fan

  DOI：10.1016/j.tet.2009.03.088

  日期：2009.6

  system with coupled catalytic cycles is described that allows radical reduction by catalyzed hydrogen atom transfer (CHAT) from transition metal hydrides. These intermediates are generated through H2 activation. Radical generation is carried out by titanocene catalyzed electron transfer to epoxides. The reaction provides a novel entry into the atom-economical reduction of radicals that has long been

  描述了具有耦合的催化循环的系统，其允许通过从过渡金属氢化物催化的氢原子转移（CHAT）进行自由基还原。这些中间体是通过H 2活化而产生的。自由基的产生是通过钛茂催化的电子转移到环氧化物上进行的。该反应为自由基的原子经济还原提供了新的途径，长期以来一直将其视为自由基化学工业应用的关键问题。
• A novel highly enantio- and diastereoselective synthesis of vitamin E side-chain
  作者：Yohei Matsueda、Shiqing Xu、Ei-ichi Negishi

  DOI：10.1016/j.tetlet.2014.12.081

  日期：2015.6

  A novel highly enantioselective (>99% ee) and diastereoselective (>98% de) method for the synthesis of chiral C15 vitamin E side-chain 1 was developed. ZACA–lipase-catalyzed acetylation protocol to provide a key α,ω-dioxyfunctional C5 synthon 6 (⩾99% ee), and two subsequent Cu-catalyzed alkyl–alkyl cross-coupling reactions of enantiomerically pure C5 iodide 4 were employed as key steps. 1H NMR analysis

  开发了一种新颖的高对映选择性（> 99％ee）和非对映选择性（> 98％de）的手性C 15维生素E侧链1合成方法。ZACA-脂肪酶催化的乙酰化方案可提供关键的α，ω-二氧基官能C 5合成子6（⩾99％ee），随后采用对映体纯C 5碘化物4的两个随后的Cu催化的烷基-烷基交叉偶联反应作为关键步骤。发现MαNP酯的1 H NMR分析是测量C 15维生素E侧链1的对映体纯度的简便方法。
• 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).
• Relative Asymmetric Induction in the Intramolecular Reaction between Alkynes and Cyclopropylcarbene−Chromium Complexes:  Stereocontrolled Synthesis of Five-Membered Rings Fused to Oxygen Heterocycles
  作者：Jingbo Yan、Jin Zhu、Julius J. Matasi、James W. Herndon

  DOI：10.1021/jo982144q

  日期：1999.2.1

  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.
• Catalytic, Highly Regio- and Chemoselective Generation of Radicals from Epoxides: Titanocene Dichloride as an Electron Transfer Catalyst in Transition Metal Catalyzed Radical Reactions
  作者：Andreas Gansäuer、Marianna Pierobon、Harald Bluhm

  DOI：10.1002/(sici)1521-3773(19980202)37:1/2<101::aid-anie101>3.0.co;2-w

  日期：1998.2.2