tert-butyl-(6-cyclohexylhex-5-ynyloxy)dimethylsilane | 195535-07-0

• 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-(6-cyclohexylhex-5-ynyloxy)dimethylsilane
• 英文别名: tert-butyl-(6-cyclohexylhex-5-ynoxy)-dimethylsilane
• CAS: 195535-07-0
• 化学式: C₁₈H₃₄OSi
• 分子量: 294.553
• InChiKey: KMAZGPLNXMYCCS-UHFFFAOYSA-N

物化性质

• 沸点：
  343.1±21.0 °C(Predicted)
• 密度：
  0.88±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.76
• 重原子数：
  20.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  tert-butyl-(6-cyclohexylhex-5-ynyloxy)dimethylsilane 在 咪唑 、 碘代三甲硅烷 、 Amberlyst 、 potassium tert-butylate 、 四丁基氟化铵 、 三氧化硫吡啶 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 氯仿 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 生成 tert-Butyl-(6-cyclohexyl-2-vinyl-hex-5-ynyloxy)-dimethyl-silane
  参考文献：
  名称：

  Sequential Cyclization/Silylation of Enynes Catalyzed by an Organoyttrium Complex

  摘要：

  The organoyttrium complex Cp*2YCH3.THF (Cp* = C5Me5) has been shown to be an effective precatalyst for the selective sequential cyclization/silylation of 1,6- and 1,7-enynes.. The catalyst's ability to insert the alkyne in preference to the alkene in a regioselective manner, combined with the high diastereoselectivity of the insertion process, yields a product with only one stereochemistry about the exocyclic olefin. The reaction proceeds under extremely mild conditions with short reaction times. Cyclization of enynes functionalized in the allylic position affords silylated carbocycles with high diastereoselectivities and excellent yields.

  DOI：

  10.1021/ja971538g
• 作为产物：
  描述：

  三环己基硼烷 、 6-(叔-丁基二甲基硅烷基氧基)-1-己炔 在 sodium hydroxide 、 正丁基锂 、 双氧水 、 碘 作用下， 生成 tert-butyl-(6-cyclohexylhex-5-ynyloxy)dimethylsilane
  参考文献：
  名称：

  Sequential Cyclization/Silylation of Enynes Catalyzed by an Organoyttrium Complex

  摘要：

  The organoyttrium complex Cp*2YCH3.THF (Cp* = C5Me5) has been shown to be an effective precatalyst for the selective sequential cyclization/silylation of 1,6- and 1,7-enynes.. The catalyst's ability to insert the alkyne in preference to the alkene in a regioselective manner, combined with the high diastereoselectivity of the insertion process, yields a product with only one stereochemistry about the exocyclic olefin. The reaction proceeds under extremely mild conditions with short reaction times. Cyclization of enynes functionalized in the allylic position affords silylated carbocycles with high diastereoselectivities and excellent yields.

  DOI：

  10.1021/ja971538g

文献信息

• Gold-Catalyzed Highly Regioselective Oxidation of C−C Triple Bonds without Acid Additives: Propargyl Moieties as Masked α,β-Unsaturated Carbonyls
  作者：Biao Lu、Chaoqun Li、Liming Zhang

  DOI：10.1021/ja1072614

  日期：2010.10.13

  Gold-catalyzed intermolecular oxidations of internal alkynes have been achieved with high regioselectivities using 8-alkylquinoline N-oxides as oxidants and in the absence of acid additives. Synthetically versatile α,β-unsaturated carbonyls are obtained in good to excellent yields and with excellent E-selectivities. A range of functional groups such as THP, MOMO, N(3), OTBS, and N-Boc are tolerated

  使用 8-烷基喹啉 N-氧化物作为氧化剂并且在没有酸添加剂的情况下，已经以高区域选择性实现了内部炔烃的金催化分子间氧化。合成通用的 α,β-不饱和羰基化合物以良好到极好的收率和极好的 E 选择性获得。可以容忍一系列功能组，例如 THP、MOMO、N(3)、OTBS 和 N-Boc。该反应允许 α,β-不饱和羰基被掩蔽为炔丙基部分，从而为复杂结构合成中可能遇到的这些官能团的相容性问题提供了实用的解决方案。