5-(tert-butyldiphenylsilanyloxy)pent-2-yn-1-al | 916484-38-3

• 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: 5-(tert-butyldiphenylsilanyloxy)pent-2-yn-1-al
• 英文别名: 5-((tertbutyldiphenylsilyl)oxy)pent-2-ynal；5-[Tert-butyl(diphenyl)silyl]oxypent-2-ynal
• CAS: 916484-38-3
• 化学式: C₂₁H₂₄O₂Si
• 分子量: 336.506
• InChiKey: VNEKGNZNEMHSLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.16
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  5-(tert-butyldiphenylsilanyloxy)pent-2-yn-1-al 在 Lindlar's catalyst 喹啉 、 重铬酸吡啶 、 4 A molecular sieve 、 potassium tert-butylate 、 四丁基氟化铵 、 氢气 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 二甲基亚砜 为溶剂， 生成 3-((1E,3E)-5,7-Dihydroxy-hepta-1,3-dienyl)-3H-isobenzofuran-1-one
  参考文献：
  名称：

  The first synthesis of the epoxide-containing macrolactone nucleus of oximidine I

  摘要：

  A synthesis of the epoxydiene-containing macrolide nucleus of oximidine I is reported, starting from commercially available 3-butyn-l-ol. The key macrocyclisation step is achieved using Homer-Wadsworth-Emmons methodology in the presence of an epoxide. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01775-1
• 作为产物：
  描述：

  5-((tert-butyldiphenylsilyl)oxy)pent-2-yn-1-ol 在 barium permanganate 作用下， 以 二氯甲烷 为溶剂， 以76%的产率得到5-(tert-butyldiphenylsilanyloxy)pent-2-yn-1-al
  参考文献：
  名称：

  Synthesis and Stability of a Homologous Series of Triynol Natural Products and Their Analogues

  摘要：

  A series of polyyne natural products 1, 13, and 31 and analogues 14, 21, and 22 are synthesized in six steps. The key step is a Fritsch-Buttenberg-Wiechell rearrangement in which a triyne framework is formed from the appropriate dibromoolefin precursor. Terminal conjugated triynes 13 and 14 are obtained as highly unstable products that rapidly decompose under ambient conditions. The stability of triynols increases via either the addition of methylene units (i.e., 6 -> 31 -> 1) or addition of terminal substituents (i.e., 13 -> 21 or 31).

  DOI：

  10.1021/jo061588g

文献信息

• De Novo Synthesis of Highly Functionalized Benzimidazolones and Benzoxazolones through an Electrochemical Dehydrogenative Cyclization Cascade
  作者：Fan Xu、Hao Long、Jinshuai Song、Hai‐Chao Xu

  DOI：10.1002/anie.201904931

  日期：2019.7

  benzoxazolone moieties are important scaffolds in a variety of pharmaceutical molecules. These bicyclic heterocycles are usually prepared from a benzene derivative through the construction of an additional five‐membered heterocyclic ring. We report herein a method that enables the efficient synthesis of highly substituted benzimidazolone and benzoxazolone derivatives by building both the benzene and the heterocyclic

  苯并咪唑酮和苯并恶唑酮部分是多种药物分子中的重要支架。这些双环杂环通常是由苯衍生物通过构建一个额外的五元杂环而制得的。我们在此报告了一种方法，该方法通过通过脱氢环化级联反应构建苯和杂环，从而能够高效合成高度取代的苯并咪唑酮和苯并恶唑酮衍生物。现成的芳基胺系的1,5-烯炔化合物经过一个双环化/脱氢级联反应，可在一个步骤中完全控制区域选择性地提供官能化的苯并萘化杂环。这些由电力驱动的氧化转化过程以H 2进行 进化，因此消除了对基于过渡金属的催化剂和氧化剂的需求。
• Copper(I)-Catalyzed Boryl Substitution of Allyl Aminals: Selective Synthesis of Linear γ-Aminoallylboronates
  作者：Hajime Ito、Yuta Takenouchi

  DOI：10.1055/s-0036-1588802

  日期：2017.11

  the Special Topic Modern Strategies for Borylation in Synthesis Abstract A novel approach for the selective synthesis of α-substituted γ-aminoallylboronates through a copper(I)-catalyzed γ-boryl-substitution of allyl aminals is developed. The reaction proceeds with high yield (up to 88%) and good E/Z selectivity (up to >95:5). Subsequent aldehyde allylation using allylboronates affords (Z)-anti-1,2-amino

  作为合成中硼化的现代策略特别主题的一部分发布 抽象的 提出了一种通过铜（I）催化的烯丙基缩醛胺选择性合成α-取代的γ-氨基烯丙基硼酸酯的新方法。反应以高收率（高达88％）和良好的E / Z选择性（高达> 95：5）进行。随后使用烯丙基硼酸酯的醛烯丙基化提供具有高立体选择性（高达91％收率，和高达17:83 E / Z）的（Z）-抗-1,2-氨基醇衍生物。 提出了一种通过铜（I）催化的烯丙基缩醛胺选择性合成α-取代的γ-氨基烯丙基硼酸酯的新方法。反应以高收率（高达88％）和良好的E / Z选择性（高达> 95：5）进行。随后使用烯丙基硼酸酯的醛烯丙基化提供具有高立体选择性（高达91％收率，和高达17:83 E / Z）的（Z）-抗-1,2-氨基醇衍生物。
• A gold(<scp>i</scp>)-catalysed approach towards harmalidine an elusive alkaloid from <i>Peganum harmala</i>
  作者：Solène Miaskiewicz、Jean-Marc Weibel、Patrick Pale、Aurélien Blanc

  DOI：10.1039/d2ra05685b

  日期：——

  natural products, was efficiently obtained from N-aryl 2-alkynylazetidine derivatives. In an attempt to apply this methodology to the synthesis of harmalidine, isolated from the seeds of Peganum harmala, advanced amino 2,3-hydropyrrolo[1,2-a]indol(one) derivatives were readily obtained in only 11 steps from but-3-yn-1-ol. While the reported structure of harmalidine could not be reached from these intermediates

  在金催化下，2,3-二氢吡咯并[1,2- a ]吲哚基序（在少数但有趣的生物活性天然产物中遇到）可以从N-芳基2-炔基氮杂环丁烷衍生物中有效获得。尝试将此方法应用于从骆驼蓬种子中分离出的骆驼蓬定的合成中，仅通过 11 个步骤即可轻松获得高级氨基 2,3-氢吡咯并[1,2- a ]吲哚（一）衍生物。 3-yn-1-ol。虽然从这些中间体无法获得已报道的骆马定结构，但令人惊讶的是分离出了 12 元二亚氨基二聚体。将报告的骆驼蓬碱 NMR 数据与我们的合成分子、骆驼蓬碱或合成的N-甲基骆驼蓬碱的实验和计算数据进行广泛比较，显示与提议的天然产物结构存在差异。
• Synthesis and Stability of a Homologous Series of Triynol Natural Products and Their Analogues
  作者：Thanh Luu、Rik R. Tykwinski

  DOI：10.1021/jo061588g

  日期：2006.11.1

  A series of polyyne natural products 1, 13, and 31 and analogues 14, 21, and 22 are synthesized in six steps. The key step is a Fritsch-Buttenberg-Wiechell rearrangement in which a triyne framework is formed from the appropriate dibromoolefin precursor. Terminal conjugated triynes 13 and 14 are obtained as highly unstable products that rapidly decompose under ambient conditions. The stability of triynols increases via either the addition of methylene units (i.e., 6 -> 31 -> 1) or addition of terminal substituents (i.e., 13 -> 21 or 31).
• The first synthesis of the epoxide-containing macrolactone nucleus of oximidine I
  作者：Joanne E. Harvey、Steven A. Raw、Richard J.K. Taylor

  DOI：10.1016/s0040-4039(03)01775-1

  日期：2003.9

  A synthesis of the epoxydiene-containing macrolide nucleus of oximidine I is reported, starting from commercially available 3-butyn-l-ol. The key macrocyclisation step is achieved using Homer-Wadsworth-Emmons methodology in the presence of an epoxide. (C) 2003 Elsevier Ltd. All rights reserved.