cis-1,4-Bis(t-Butyldimethylsilyl)cyclopent-2-ene-1,4-diol | 61692-11-3

• 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: cis-1,4-Bis(t-Butyldimethylsilyl)cyclopent-2-ene-1,4-diol
• 英文别名: is-3,5-bis((tert-butyldimethylsilyl)oxy)cyclopent-1-ene；3,5-bis((tert-butyldimethylsilyl)oxy)cyclopent-1-ene；tert-butyl-[(1S,4R)-4-[tert-butyl(dimethyl)silyl]oxycyclopent-2-en-1-yl]oxy-dimethylsilane
• CAS: 61692-11-3
• 化学式: C₁₇H₃₆O₂Si₂
• 分子量: 328.643
• InChiKey: NFJLUMGGLUDOKL-GASCZTMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.73
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-1,4-Bis(t-Butyldimethylsilyl)cyclopent-2-ene-1,4-diol 在 水 、 碳酸氢钠 、 溶剂黄146 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 78.5h， 生成 (1R,2R,4S,5S)-6-氧杂双环[3.1.0]己烷-2,4-二基二乙酸酯
  参考文献：
  名称：

  Lipase-catalyzed transesterification of meso-cyclopentane diols

  摘要：

  The lipase-catalyzed transesterification of the meso-cyclopentane diols 1a - 6a with vinyl acetate in tetrahydrofuran/triethylamine in the presence of lipases of different origin has been investigated. Depending on the structure of the substrate and the origin of the lipase chiral cyclopentane derivatives with high enantiomeric excess could be obtained in good to excellent chemical yields.

  DOI：

  10.1016/s0040-4020(01)88281-8
• 作为产物：
  描述：

  环戊二烯 在 咪唑 、 氧气 、 rose bengal 、 硫脲 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 40.0h， 生成 cis-1,4-Bis(t-Butyldimethylsilyl)cyclopent-2-ene-1,4-diol
  参考文献：
  名称：

  宝石-二溴环丙烷扩环/Mizoroki-Heck 环化路线生成四氢二苯并呋喃

  摘要：

  容易获得的氧化 6,6-二溴双环[3.1.0]己烷与异香草醛进行开环/亲核捕获反应，得到加合物，该加合物可以参与分子内 Mizoroki-Heck 反应，得到四氢二苯并呋喃。进行反应顺序第一步的方式的变化可用于改变中间体和最终产物的区域化学形式和立体化学形式。

  DOI：

  10.1002/ejoc.202400038

文献信息

• Synthetic Studies on Bilobalide
  作者：Akihiro Shiogai、Tatsuya Toma、Satoshi Yokoshima

  DOI：10.1055/s-0039-1691559

  日期：2020.2

  We disclose our synthetic studies on bilobalide, which features a Diels–Alder reaction of a cyclic anhydride to form two contiguous quaternary carbon centers, desymmetrization of a symmetric diol, and construction of a cyclic acetal under acidic conditions with inversion of configuration at an allylic position.

  我们公开了我们对 bilobalide 的合成研究，其特征是环状酸酐的 Diels-Alder 反应形成两个连续的季碳中心，对称二醇的去对称化，以及在酸性条件下构建环状缩醛，在烯丙基位置发生构型反转.
• Stereoselective Synthesis of 3-Hydroxy-4-arylcyclopentanones and 4-Arylcyclopentenones through a Heck-Matsuda Desymmetrization of<i>meso cis</i>-4-Cyclopentene-1,3-diol
  作者：Rafaela C. Carmona、Carlos Roque D. Correia

  DOI：10.1002/adsc.201500281

  日期：2015.8.24

  enantioselective manner by a Heck–Matsuda desymmetrization was achieved from the commercially available meso cis‐4‐cyclopentene‐1,3‐diol. This method is highly practical, mild, high yielding and is carried out under “open vessel” conditions. Protected and unprotected substrates provide distinct products bearing considerable value as synthetic scaffolds for the synthesis of natural and unnatural bioactive

  从市场上可买到的内消旋顺式-4-环戊烯-1,3-二醇，通过Heck-Matsuda脱对称反应，以非对映和对映选择性的方式，将钯催化合成3-羟基-4-芳基环戊烯酮和4-芳基环戊烯酮。该方法是高度实用，温和，高产的，并且在“开放容器”条件下进行。受保护和不受保护的底物可提供独特的产品，具有可观的价值，可作为合成支架的天然骨架和不自然的含有五元环的生物活性化合物的合成。
• Synthetic Efforts toward the C22−C36 Subunit of Halichondrin B Utilizing Local and Imposed Symmetry
  作者：Valerie A. Keller、Ikyon Kim、Steven D. Burke

  DOI：10.1021/ol0473400

  日期：2005.2.1

  C22-C34 portion (2) of halichondrin B was synthesized from meso-symmetric bis-silyl protected cyclopentenediol (7) in 20 steps and 7% overall yield. This was accomplished through a two-directional synthesis/terminus differentiation strategy that proceeded via achiral, meso-symmetric intermediates for eight steps and employed a Pd(0)-mediated asymmetric double cycloetherification to establish both tetrahydropyran

  卤虫草酮B的C22-C34部分（2）是由内对称的双甲硅烷基保护的环戊二醇（7）以20个步骤合成的，总收率为7％。这是通过双向合成/末端分化策略完成的，该策略通过非手性，内消旋中间体进行了八步操作，并采用Pd（0）介导的不对称双环醚化作用来建立两个四氢吡喃环。[结构：看文字]
• An Efficient Protocol for Selective Silylation of Hydroxy Group Using <i>N</i>,<i>O</i>-Bis(<i>tert</i>-butyldimethylsilyl)acetamide and <i>N</i>,<i>N</i>-Dimethyl-4-aminopyridine <i>N</i>-Oxide
  作者：Hiroki Mandai、Yuichiro Matsuura、Fatin Mahfuzah Binti Johari、Koichi Mitsudo、Seiji Suga

  DOI：10.1246/cl.220281

  日期：2022.9.5

  achieved with high chemoselectivity. In addition, several control experiments revealed that a phenolic hydroxy group was silylated much faster than a primary alcohol in both an inter- and intramolecular manner. The reactivity toward silylation under these systems might stem from the pKa of the hydroxy group.

  使用N , O-双（叔丁基二甲基甲硅烷基）乙酰胺 (BTBSA) 和 3 mol% 的N , N-二甲基-4-氨基吡啶N-氧化物 (DMAPO)开发了一种有效的醇甲硅烷基化方法。1,2-二醇的单甲硅烷基化成功地实现了高化学选择性。此外，一些对照实验表明，无论是分子间还是分子内，酚羟基的甲硅烷基化都比伯醇快得多。在这些系统下对甲硅烷基化的反应可能源于羟基的p Ka。
• Chiral induction in cyclopentyl-derived 1,3-meso-diesters: enantioselective hydrolyses with electric eel acetylcholinesterase
  作者：Donald R Deardorff、Roberto B Amador、James W Morton、Henry Y Kim、Cullen M Taniguchi、Arnel A Balbuena、Sam A Warren、Vadim Fanous、S.W.Tina Choe

  DOI：10.1016/s0957-4166(99)00236-0

  日期：1999.6

  Eight 1,3-meso-diesters derived from a common cyclopentyl backbone were exposed to the hydrolase enzyme acetylcholinesterase from Electrophorus electricus. All eight compounds were hydrolyzed by the enzyme. The overall enantioselectivities were quite high, and the resulting e.e.s were generally >90%. The absolute configurations of the product monoesters were determined through stereochemical correlation. These data revealed that the preferred site for enzymatic hydrolysis in seven of the substrates was the pro-S ester function, with pro-R cleavage detected in the eighth. (C) 1999 Elsevier Science Ltd. All rights reserved.