triisopropyl(3-methylnona-1,2-dien-1-yl)silane | 1448195-56-9

• 分子结构分类: 有机化合物 - 有机金属化合物
• 英文名称: triisopropyl(3-methylnona-1,2-dien-1-yl)silane
• CAS: 1448195-56-9
• 化学式: C₁₉H₃₈Si
• 分子量: 294.596
• InChiKey: MSUCBWCIXXHRSU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.28
• 重原子数：
  20.0
• 可旋转键数：
  9.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  triisopropyl(3-methylnona-1,2-dien-1-yl)silane 在 溶剂黄146 、 sodium nitrite 作用下， 以 氯仿 为溶剂， 反应 3.0h， 以85%的产率得到C₁₉H₃₈N₂O₃Si
  参考文献：
  名称：

  Nitration of Silyl Allenes To Form Functionalized Nitroalkenes

  摘要：

  An efficient nitration of silyl allenes with nitrogen dioxide radical, generated from NaNO2 and AcOH, to form alpha-nitro-alpha,beta-unsaturated silyl oximes has been developed. A similar nitration could be achieved by using Fe(NO3)(3)center dot 9H(2)O and FeCl3 center dot 6H(2)O, but different from the regioselective oxime formation, two regioisomeric chloride-trapped products were isolated with varying ratios depending on the steric bulk of the silyl group. A novel ring-closure reaction of alpha-nitro-alpha,beta-unsaturated silyl oximes upon treating with TBAF to form isooxazolidinone derivatives was also developed.

  DOI：

  10.1021/ol401735v
• 作为产物：
  描述：

  C₁₈H₃₆OSi 在 四甲基乙二胺 、 叔丁基锂 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 triisopropyl(3-methylnona-1,2-dien-1-yl)silane
  参考文献：
  名称：

  Nitration of Silyl Allenes To Form Functionalized Nitroalkenes

  摘要：

  An efficient nitration of silyl allenes with nitrogen dioxide radical, generated from NaNO2 and AcOH, to form alpha-nitro-alpha,beta-unsaturated silyl oximes has been developed. A similar nitration could be achieved by using Fe(NO3)(3)center dot 9H(2)O and FeCl3 center dot 6H(2)O, but different from the regioselective oxime formation, two regioisomeric chloride-trapped products were isolated with varying ratios depending on the steric bulk of the silyl group. A novel ring-closure reaction of alpha-nitro-alpha,beta-unsaturated silyl oximes upon treating with TBAF to form isooxazolidinone derivatives was also developed.

  DOI：

  10.1021/ol401735v

文献信息

• Complementary Iron(II)‐Catalyzed Oxidative Transformations of Allenes with Different Oxidants
  作者：Venkata R. Sabbasani、Hyunjin Lee、Yuanzhi Xia、Daesung Lee

  DOI：10.1002/anie.201510006

  日期：2016.1.18

  Substituent‐ and oxidant‐dependent transformations of allenes are described. Given the profound influence of the substituent on the reactivity of allenes, the subtle differences in allene structures are manifested in the formation of diverse products when reacted with different electrophiles/oxidants. In general, reactions of nonsilylated allenes involve an allylic cation intermediate by forming a

  描述了丙二烯的取代基和氧化剂依赖性转化。考虑到取代基对丙二烯反应性的深远影响，当与不同的亲电试剂/氧化剂反应时，丙二烯结构的细微差异体现在各种产物的形成中。通常，非甲硅烷基化的丙二烯的反应通过与杂化的C2形成DD键（2,3-二氯-5,6-二氰基对苯醌）或TBHP（通过在杂化C2上形成C-O键）来涉及烯丙基阳离子中间体。叔丁基过氧化氢）中，用的FeCl沿2 ⋅4ħ 2O（10摩尔％）。相反，甲硅烷基化丙二烯青睐炔阳离子中间体的由丙二烯氢化物转移到氧化剂，从而产生1,3-烯炔（E1产品）或丙炔醚THBP（S形成Ñ 1个产物）。DFT计算强烈支持由非甲硅烷基化和甲硅烷基化的丙二烯形成这些不同的假定阳离子中间体。