3-methyl-1-(tert-butyldimethylsilyloxy)-4-pentyne | 204760-53-2

• 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-methyl-1-(tert-butyldimethylsilyloxy)-4-pentyne
• 英文别名: Tert-butyl-dimethyl-(3-methylpent-4-ynoxy)silane
• CAS: 204760-53-2
• 化学式: C₁₂H₂₄OSi
• 分子量: 212.407
• InChiKey: SGMUZRGVCJZOCD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.67
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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-methyl-1-(tert-butyldimethylsilyloxy)-4-pentyne 在 正丁基锂 、 三氟化硼乙醚 作用下， 生成 (4R,4aS,5S)-4,5-dimethyl-3,4,4a,5-tetrahydro-2H-cyclopenta[b]pyran-6-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：

  1-(tert-butyldimethylsiloxy)-3-methyl-3-butene 在 正丁基锂 、 硼烷四氢呋喃络合物 、 草酰氯 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 锌 作用下， 生成 3-methyl-1-(tert-butyldimethylsilyloxy)-4-pentyne
  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

• Gold(I)‐Catalyzed Bis‐Cyclization of Allenynes for the Synthesis of Strained and Planar Polycyclic Compounds
  作者：Hitomi Tsuno、Jingfeng Shen、Hiroki Komatsu、Norihito Arichi、Shinsuke Inuki、Hiroaki Ohno

  DOI：10.1002/anie.202307532

  日期：2023.8.28

  A gold-catalyzed cascade cyclization of naphthalene-tethered allenynes gave 4H-cyclopenta[def]phenanthrene (CPP) derivatives. The reaction proceeds through the nucleophilic reaction of an alkyne with the activated allene to generate a vinyl cation intermediate followed by arylation. Selective formation of CPP and dibenzofluorene derivatives using aryl-substituted substrates, depending on the reaction

  金催化的萘系联烯炔级联环化得到 4 H -环戊[ def ]菲 (CPP) 衍生物。该反应通过炔烃与活化丙二烯的亲核反应进行，生成乙烯基阳离子中间体，然后进行芳基化。还介绍了根据反应条件，使用芳基取代的底物选择性形成 CPP 和二苯并芴衍生物。
• A remarkable ene-like reaction: Development and synthetic applications
  作者：Marco A. Ciufolini、Melissa V. Deaton、Shuren Zhu、Mingying Chen

  DOI：10.1016/s0040-4020(97)01016-8

  日期：1997.12

  A catalytic ene-like reaction of aldehydes with those vinyl ethers that display the oxygen functionality at the central carbon of an allylic system, e.g., 2-methoxypropene, is discussed in detail. The reaction is promoted by 0.05 eguiv. of the 1:1 complex of Yb(fod)(3) and acetic acid, and it is forms the centerpiece of our synthesis of chlorovulone II, mitomycinoids and phyllanthocin. (C) 1997 Elsevier Science Ltd.