(2-(chloromethyl)-1-cyclohexen-1-yl)trimethylsilane | 156518-20-6

• 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: (2-(chloromethyl)-1-cyclohexen-1-yl)trimethylsilane
• 英文别名: [2-(Chloromethyl)cyclohexen-1-yl]-trimethylsilane
• CAS: 156518-20-6
• 化学式: C₁₀H₁₉ClSi
• 分子量: 202.799
• InChiKey: FUKQVLOMILWBNQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.97
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (2-(chloromethyl)-1-cyclohexen-1-yl)trimethylsilane 在 copper(l) iodide 、 氧气 、 tetraphenylporphyrin 作用下， 以 氘代氯仿 为溶剂， 反应 5.58h， 生成 2-戊基环己-2-烯-1-酮
  参考文献：
  名称：

  Regioselectivity of the Singlet Oxygen Ene Reaction (Schenck Reaction) with Vinylsilanes

  摘要：

  The ene reaction-of singlet oxygen and vinylsilanes 1 with various substitution patterns and double-bond geometry has been studied. beta-Silyl allylic hydroperoxides 2 were the major products of the photooxygenation, accompanied by smaller amounts of alpha,beta-unsaturated ketones 3. The latter derive from decomposition of the regioisomeric alpha-hydroperoxy silanes 4 by elimination of silanol. Regioselectivities up to 97:3 were observed for vinylsilanes with a methyl group geminal to the silyl group and with cyclic derivatives. Z-Configurated substrates showed lower regioselectivity and reactivity. Elongation of the carbon chain at the geminal position also increased the amount enone formed. These results are rationalized in terms of stereoelectronic effects imposed by the silyl group on the ring-opening of the perepoxide intermediate.

  DOI：

  10.1021/jo00091a020
• 作为产物：
  描述：

  (2-chloro-1-cyclohexen-1-yl)methanol 在 盐酸 、 四氯化碳 、 三甲基氯硅烷 、 sodium 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 14.78h， 生成 (2-(chloromethyl)-1-cyclohexen-1-yl)trimethylsilane
  参考文献：
  名称：

  Highly Regio- and Diastereoselective One-Pot Synthesis of Silyl Epoxy Alcohols and Vinylsilanes by Direct Hydroxy-Epoxidation

  摘要：

  A direct synthesis of silyl epoxy alcohols from vinyl silanes is described. It consists of the regioselective ene reaction of the vinylsilanes with singlet oxygen, which proceeds with predominant hydrogen abstraction at the position geminal to the silyl group. The resulting silyl allylic hydroperoxides were treated, without isolation, subsequently with Ti(O-i-Pr)(4) to afford the silyl epoxy alcohols in good yields and very high diastereomeric ratios, which ranged from 93:7 to greater than 97:3. Alternatively, the vinylsilanes were photooxygenated directly in the presence of the titanium catalyst and the silyl epoxy alcohols obtained in good yields. The method was applied to di- and trisubstituted acyclic vinylsilanes with a methyl group geminal to silicon and cyclic derivatives all give consistently good results. In this novel hydroxy-epoxidation, the regioselectivity of the singlet oxygen ene reaction as well as the diastereoselectivity of the oxygen transfer can be controlled by the steering effects of the silyl group.

  DOI：

  10.1021/jo00091a021

文献信息

• Regioselectivity of the Singlet Oxygen Ene Reaction (Schenck Reaction) with Vinylsilanes
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1021/jo00091a020

  日期：1994.6

  The ene reaction-of singlet oxygen and vinylsilanes 1 with various substitution patterns and double-bond geometry has been studied. beta-Silyl allylic hydroperoxides 2 were the major products of the photooxygenation, accompanied by smaller amounts of alpha,beta-unsaturated ketones 3. The latter derive from decomposition of the regioisomeric alpha-hydroperoxy silanes 4 by elimination of silanol. Regioselectivities up to 97:3 were observed for vinylsilanes with a methyl group geminal to the silyl group and with cyclic derivatives. Z-Configurated substrates showed lower regioselectivity and reactivity. Elongation of the carbon chain at the geminal position also increased the amount enone formed. These results are rationalized in terms of stereoelectronic effects imposed by the silyl group on the ring-opening of the perepoxide intermediate.
• Highly Regio- and Diastereoselective One-Pot Synthesis of Silyl Epoxy Alcohols and Vinylsilanes by Direct Hydroxy-Epoxidation
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1021/jo00091a021

  日期：1994.6

  A direct synthesis of silyl epoxy alcohols from vinyl silanes is described. It consists of the regioselective ene reaction of the vinylsilanes with singlet oxygen, which proceeds with predominant hydrogen abstraction at the position geminal to the silyl group. The resulting silyl allylic hydroperoxides were treated, without isolation, subsequently with Ti(O-i-Pr)(4) to afford the silyl epoxy alcohols in good yields and very high diastereomeric ratios, which ranged from 93:7 to greater than 97:3. Alternatively, the vinylsilanes were photooxygenated directly in the presence of the titanium catalyst and the silyl epoxy alcohols obtained in good yields. The method was applied to di- and trisubstituted acyclic vinylsilanes with a methyl group geminal to silicon and cyclic derivatives all give consistently good results. In this novel hydroxy-epoxidation, the regioselectivity of the singlet oxygen ene reaction as well as the diastereoselectivity of the oxygen transfer can be controlled by the steering effects of the silyl group.