1,4-bis(tert-butyldiphenylsilyl)buta-1,3-diyne | 1236153-61-9

• 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: 1,4-bis(tert-butyldiphenylsilyl)buta-1,3-diyne
• 英文别名: Tert-butyl-[4-[tert-butyl(diphenyl)silyl]buta-1,3-diynyl]-diphenylsilane
• CAS: 1236153-61-9
• 化学式: C₃₆H₃₈Si₂
• 分子量: 526.869
• InChiKey: PUMWQBUQPGICLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  38
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,4-bis(tert-butyldiphenylsilyl)buta-1,3-diyne 在 1,1-bis(cyclopentadienyl)-2-ethyl-1-zirconacyclopropane(IV) 、 甲醇 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以61%的产率得到
  参考文献：
  名称：

  锆茂介导的1，3-丁二炔与醛的偶联高效合成顺式[[3]异丙苯二酚

  摘要：

  已经开发出使用Negishi试剂的甲硅烷基-或叔丁基-取代的1，3-丁二炔单锆化的高效且方便的方法。所得的丁二烯锆配合物与各种醛进行两个syn-S E 2'反应，生成具有中等至高非对映选择性的顺式-[3]枯烯二醇。丁二炔末端的甲硅烷基取代基对非对映选择性具有显着影响。

  DOI：

  10.1021/om201125z
• 作为产物：
  描述：

  tert-butyldiphenylsilylacetylene 在 nickel(II) iodide 、 锰 、 N-溴代丁二酰亚胺(NBS) 、 silver nitrate 作用下， 以 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 75.0h， 生成 1,4-bis(tert-butyldiphenylsilyl)buta-1,3-diyne
  参考文献：
  名称：

  Nickel-Catalyzed Reductive 1,2-Dialkynylation of Alkenes Bearing an 8-Aminoquinoline Directing Group

  摘要：

  An unprecedented nickel-catalyzed reductive 1,2-dialkynylation of alkenes bearing an 8-aminoquinoline directing group has been developed. This method proceeded through a migratory insertion/reductive-coupling process under mild conditions with a wide substrate scope and good functional group tolerance, providing direct access to the synthetically flexible 1,5-diynes. Moreover, the 1,2-dialkynylation products could be further converted to borate-ester- or azide-functionalized 1,5-dienes, ditriazole, beta-diyne primary amide, and trisubstituted benzene.

  DOI：

  10.1021/acs.orglett.9b03147

文献信息

• Zirconium-Mediated Multicomponent Reactions of 1,3-Butadiynes with Ylidenemalononitriles to Form Functionalized 1,8-Naphthyridine and Cyclopenta[<i>b</i>]pyridine Derivatives
  作者：Shasha Yu、Renhong Sun、Haoyi Chen、Xin Xie、Yuanhong Liu

  DOI：10.1002/chem.201405899

  日期：2015.1.19

  Zirconocene‐mediated multicomponent reactions of 1,3‐butadiynes with ylidenemalononitriles in the absence or presence of CuCl have been developed. In the absence of CuCl, 1,3‐butadiyne couples with three molecules of ylidenemalononitriles to yield azazirconacycles bearing a hexahydro‐1,8‐naphthyridine skeleton with high stereoselectivity. In the presence of CuCl, cyclopenta[b]pyridine or cyclopenta[b]quinolin‐1‐one

  在不存在或存在CuCl的情况下，已开发出由茂茂锆介导的1,3-丁二炔与亚甲基丙二腈的多组分反应。在没有CuCl的情况下，1,3-丁二炔与三个分子的亚甲基丙二腈偶合，生成具有六氢-1,8-萘啶骨架且具有高立体选择性的氮杂碳杂环。在氯化亚铜，环戊二烯并[存在b ]吡啶或环戊二烯并[ b ]喹啉-1-酮衍生物通过Zr中的转移金属化获得 C键与Cu  C键作为键反应步骤。这些多米诺型反应继续进行具有高化学-选择性，区域选择性和/或立体选择性，并允许多个C形成 N和C  C键在单个操作中。
• Stereoselective synthesis of enynones via base-catalyzed isomerization of 1,5-disubstituted-2,4-pentadiynyl silyl ethers or their alcohol derivatives
  作者：Jingjin Chen、Guoqin Fan、Yuanhong Liu

  DOI：10.1039/c0ob00344a

  日期：——

  1,5-Disubstituted-2,4-pentadiynyl silyl ethers undergo smooth desilylative isomerization to afford cis-enynones as major products with moderate stereoselectivities in the presence of a catalytic amount of KOtBu or DBU. While the isomerization reactions of their alcohol derivatives catalyzed by KOH, KOtBu or NaH take place efficiently to produce trans-enynones with high stereoselectivities. These reactions

  1,5-二取代的2,4-戊二炔基甲硅烷基醚经过顺式脱甲硅烷基化异构化反应，以顺式-乙炔酮为主要产物，并在催化量的二甲基甲酰胺存在下，具有中等的立体选择性。KO Ť卜 或者 DBU。而其醇衍生物的异构化反应是通过酸值， KO Ť卜 或者 碳酸氢钠有效地产生具有高立体选择性的反式-乙炔酮。这些反应为合成具有广泛取代基的烯酮提供了方便实用的途径。
• Unexpected Zirconium-Mediated Multicomponent Reactions of Conjugated 1,3-Butadiynes and Monoynes with Acyl Cyanide Derivatives
  作者：Shasha Yu、Xu You、Yuanhong Liu

  DOI：10.1002/chem.201202607

  日期：2012.10.29

  Going ber(zirc): Zirconium–butadiyne complexes react with acyl cyanide derivatives through diverse reaction pathways. The complexes react with two molecules of carbamoyl cyanide to form 1,4‐benzodiazepin‐2‐one‐derivatives containing azazirconacycles. Reactions with either aroyl cyanides or alkyl cyanoformates lead to azazirconacyclopentenes containing a quaternary carbon center.

  趋于ber（zirc）：锆-丁二炔配合物通过多种反应途径与酰基氰化物衍生物反应。该络合物与两个氨基甲酰氰分子反应形成含有氮杂锆并环的1,4-苯并二氮杂-2-2-1衍生物。与芳酰基氰化物或烷基氰甲酸酯的反应导致形成具有季碳中心的氮杂氮杂萘环戊烯。
• Highly Efficient Synthesis of <i>cis</i>-[3]Cumulenic Diols via Zirconocene-Mediated Coupling of 1,3-Butadiynes with Aldehydes
  作者：Xiaoping Fu、Shasha Yu、Guoqin Fan、Yuanhong Liu、Yuxue Li

  DOI：10.1021/om201125z

  日期：2012.1.23

  A highly efficient and convenient method for the monozirconation of silyl- or tert-butyl-substituted 1,3-butadiynes using the Negishi reagent has been developed. The resulting zirconium butadiyne complexes undergo two syn-SE2′ reactions with various aldehydes to yield the cis-[3]cumulenic diols with moderate to high diastereoselectivities. The silyl substituents at the butadiyne terminus show remarkable

  已经开发出使用Negishi试剂的甲硅烷基-或叔丁基-取代的1，3-丁二炔单锆化的高效且方便的方法。所得的丁二烯锆配合物与各种醛进行两个syn-S E 2'反应，生成具有中等至高非对映选择性的顺式-[3]枯烯二醇。丁二炔末端的甲硅烷基取代基对非对映选择性具有显着影响。
• Nickel-Catalyzed Reductive 1,2-Dialkynylation of Alkenes Bearing an 8-Aminoquinoline Directing Group
  作者：Rui Pan、Cong Shi、Dongquan Zhang、Yang Tian、Songjin Guo、Hequan Yao、Aijun Lin

  DOI：10.1021/acs.orglett.9b03147

  日期：2019.11.15

  An unprecedented nickel-catalyzed reductive 1,2-dialkynylation of alkenes bearing an 8-aminoquinoline directing group has been developed. This method proceeded through a migratory insertion/reductive-coupling process under mild conditions with a wide substrate scope and good functional group tolerance, providing direct access to the synthetically flexible 1,5-diynes. Moreover, the 1,2-dialkynylation products could be further converted to borate-ester- or azide-functionalized 1,5-dienes, ditriazole, beta-diyne primary amide, and trisubstituted benzene.