Tert-butyl-[2-(cyclohexen-1-yl)ethynyl]-dimethylsilane | 937058-20-3

• 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: Tert-butyl-[2-(cyclohexen-1-yl)ethynyl]-dimethylsilane
• CAS: 937058-20-3
• 化学式: C₁₄H₂₄Si
• 分子量: 220.43
• InChiKey: APCJIRDVPSXHQE-UHFFFAOYSA-N

物化性质

• 沸点：
  269.2±19.0 °C(Predicted)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.54
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  Tert-butyl-[2-(cyclohexen-1-yl)ethynyl]-dimethylsilane 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以82%的产率得到(1R*,2R*)-1-[2-(tert-butyldimethylsilyl)ethynyl]-7-oxabicyclo[4.1.0]heptane
  参考文献：
  名称：

  Palladium-Catalyzed Diastereoselective Coupling of Propargylic Oxiranes with Terminal Alkynes

  摘要：

  A diastereoselective coupling of propargylic oxiranes with terminal alkynes has been developed with use of a palladium catalyst. The stereochemistries of the resulting 4-alkynyl-substituted 2,3-allenols have been altered depending on the palladium catalyst. An optically active anti-substituted allene was synthesized from the reaction of an enantiomerically enriched propargylic oxirane without loss of chirality.

  DOI：

  10.1021/ol070224n
• 作为产物：
  描述：

  1-[2-[Tert-butyl(dimethyl)silyl]ethynyl]cyclohexan-1-ol 在 三氯氧磷 作用下， 以 吡啶 为溶剂， 以76%的产率得到Tert-butyl-[2-(cyclohexen-1-yl)ethynyl]-dimethylsilane
  参考文献：
  名称：

  Palladium-Catalyzed Diastereoselective Coupling of Propargylic Oxiranes with Terminal Alkynes

  摘要：

  A diastereoselective coupling of propargylic oxiranes with terminal alkynes has been developed with use of a palladium catalyst. The stereochemistries of the resulting 4-alkynyl-substituted 2,3-allenols have been altered depending on the palladium catalyst. An optically active anti-substituted allene was synthesized from the reaction of an enantiomerically enriched propargylic oxirane without loss of chirality.

  DOI：

  10.1021/ol070224n

文献信息

• Manganese/Cobalt Bimetallic Relay Catalysis for Divergent Dehydrogenative Difluoroalkylation of Alkenes
  作者：Tao Zhong、Chengyihan Gu、Yuhang Li、Jun Huang、Jian Han、Chengjian Zhu、Jie Han、Jin Xie

  DOI：10.1002/anie.202310762

  日期：2023.10.16

  The involvement of manganese radical for halogen atom transfer (XAT) reactions has been esteemed as one reliable method but encountered with limited catalytic models. In this paper, a novel bimetallic relay catalysis of Mn₂(CO)₁₀ and cobaloxime has been developed for divergent dehydrogenative difluoroalkylation of alkenes using commercially available difluoroalkyl bromides. A wide range of structurally diverse terminal, cyclic and internal alkenes as well as tetrasubstituted alkenes are found to be good coupling partners to deliver difluoroalkylated allylic products and difluoromethylated cyclic products, accompanied with the production of H₂ as the by‐product. This bimetallic relay strategy features broad substrate scope, mild reaction conditions and excellent functional group compatibility. Its success represents an important step‐forward to expedite the construction of a rich library of difluoroalkylated products.

  摘要锰自由基参与卤原子转移（XAT）反应一直被认为是一种可靠的方法，但催化模型有限。本文开发了一种新型的 Mn2(CO)10 和钴肟双金属接力催化法，用于使用市售的二氟烷基溴对烯烃进行歧化脱氢二氟烷基化反应。研究发现，多种结构不同的末端、环状和内部烯烃以及四取代烯烃都是良好的偶联伙伴，可提供二氟烷基化烯丙基产物和二氟甲基化环状产物，并产生 H2 作为副产品。这种双金属中继策略具有广泛的底物范围、温和的反应条件和出色的官能团兼容性。它的成功为加快构建丰富的二氟烷基化产物库迈出了重要一步。
• 1,2-Silyl Rearrangement in Gold Carbene Chemistry: Synthesis of Furyl-Decorated Tetrasubstituted Silylallene Derivatives
  作者：Patricia García-Martínez、Luis A. López

  DOI：10.1021/acs.orglett.4c01468

  日期：2024.6.7

  The gold-catalyzed reaction of 2-en-4-ynones with alkynylsilanes provides fully substituted allene derivatives bearing furyl and silyl groups. This transformation would involve generation of a gold furyl carbene intermediate, which regioselectively undergoes a nucleophilic attack by the alkynylsilane at the electrophilic carbene carbon atom with the formation of a β-gold vinyl cation species. The subsequent

  2-en-4-炔酮与炔基硅烷的金催化反应提供带有呋喃基和甲硅烷基的完全取代的丙二烯衍生物。这种转化将涉及金呋喃基卡宾中间体的生成，该中间体区域选择性地经历炔基硅烷对亲电子卡宾碳原子的亲核攻击，形成β-金乙烯基阳离子物质。随后金催化剂的释放，伴随着 1,2-甲硅烷基转移，导致四取代丙二烯产物的形成。