(4,4-dibromo-3-(4-methoxyphenyl)but-3-en-1-yn-1-yl)trimethylsilane | 405064-51-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (4,4-dibromo-3-(4-methoxyphenyl)but-3-en-1-yn-1-yl)trimethylsilane
• 英文别名: [4,4-Dibromo-3-(4-methoxyphenyl)but-3-en-1-ynyl]-trimethylsilane
• CAS: 405064-51-9
• 化学式: C₁₄H₁₆Br₂OSi
• 分子量: 388.174
• InChiKey: HSYWLHQWJLJJPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.03
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  (4,4-dibromo-3-(4-methoxyphenyl)but-3-en-1-yn-1-yl)trimethylsilane 在 碲化氢 、 sodium tetrahydroborate 作用下， 以 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 2.0h， 以39%的产率得到4-(4-methoxyphenyl)-2-(trimethylsilyl)tellurophene
  参考文献：
  名称：

  Cascade and Effective Syntheses of Functionalized Tellurophenes

  摘要：

  A one-pot and transition-metal-catalyst-free synthetic strategy to construct functionalized tellurophenes has been developed. Substituted 1,1-dibromo-l-en-3-ynes are smoothly converted to tellurophenes with telluride salts in high yield via a series of cascade reactions through reductive debromination, hydrotelluration, nucleophilic cyclization, and aromatization. Close inspection of the results clearly showed that the reactivity of in situ prepared telluride salts are significantly influenced by the polarity of the solvent system and the electronic nature of the substituent on the enyne substrate. This method reports the first direct synthesis of 3-aryltellurophenes in high yields at room temperature. This novel reaction strategy is also found to be a promising synthetic method for multisubstituted tellurophenes and selenophenes.

  DOI：

  10.1021/acs.orglett.8b00279
• 作为产物：
  描述：

  1-(4-methoxyphenyl)-3-(trimethylsilyl)-prop-2-yn-1-one 在 四溴化碳 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 生成 (4,4-dibromo-3-(4-methoxyphenyl)but-3-en-1-yn-1-yl)trimethylsilane
  参考文献：
  名称：

  Chiral Propargyl Alcohols via the Enantioselective Addition of Terminal Di- and Triynes to Aldehydes

  摘要：

  The enantioselective addition of di- and triynes to aldehydes is presented, including the first examples of an asymmetric triyne addition. Modification of the Carreira alkynylation protocol shows that addition of diynes and triynes to alpha-branched aldehydes can be complete in as little as 4 h, and these reactions give good yields and enantioselectivities (up to 98% ee) for di- and triynes tested (aryl, alkyl, and silyl). It is shown for two cases (20 and 24) that products of this asymmetric addition reaction can undergo further manipulation (desilylation and triazole formation) without affecting the enantiopurity.

  DOI：

  10.1021/jo2008719

文献信息

• Synthesis of Unsymmetrically Substituted 1,3-Butadiynes and 1,3,5-Hexatriynes via Alkylidene Carbenoid Rearrangements
  作者：Annabelle L. K. Shi Shun、Erin T. Chernick、Sara Eisler、Rik R. Tykwinski

  DOI：10.1021/jo026481h

  日期：2003.2.1

  Unsymmetrically substituted 1,3-butadiynes and 1,3,5-hexatriynes are synthesized in four steps from commercially available aldehydes or carboxylic acids. The key step in this process involves a Fritsch-Buttenberg-Wiechell rearrangement, in which an alkylidene carbenoid intermediate subsequently rearranges to the desired polyyne. This rearrangement proceeds under mild conditions, and it is tolerant

  不对称取代的1,3-丁二炔和1,3,5-己三炔由市售的醛或羧酸分四个步骤合成。该过程中的关键步骤涉及Fritsch-Buttenberg-Wiechell重排，其中亚烷基类胡萝卜素中间体随后重排为所需的多炔。这种重排在温和的条件下进行，并且可以耐受一系列功能。通常，在程序上容易形成二溴代烯烃前体，再加上重排步骤的有效性，使得该方法成为利用钯或铜催化的传统的二炔和三炔合成方法的有吸引力的替代方法。
• Modification of the Fritsch–Buttenberg–Wiechell rearrangement: a facile route to unsymmetrical butadiynes
  作者：Erin T Chernick、Sara Eisler、Rik R Tykwinski

  DOI：10.1016/s0040-4039(01)01901-3

  日期：2001.12

  echell rearrangement has been used to form unsymmetrically substituted 1,3-butadiynes from 1,1-dibromo-olefin precursors. The reaction proceeds via lithium–halogen exchange, followed by migration of the aryl or alkynyl moiety to provide the butadiyne framework. The facile formation of the dibromo-olefins in three steps from commercially available aryl aldehydes or carboxylic acid chlorides makes this

  Fritsch–Buttenberg–Wiechell重排的一种修饰已用于从1,1-二溴烯烃前体形成不对称取代的1,3-丁二炔。反应通过锂-卤素交换进行，然后芳基或炔基部分迁移以提供丁二炔骨架。由市售的芳基醛或羧酸氯化物分三步轻松形成二溴代烯烃，使该方法成为传统丁二炔合成方法的有吸引力的替代方法。