(1,7-dioxaspiro[5.5]undec-4-en-2-ylmethoxy)(tert-butyl)diphenylsilane

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1,7-dioxaspiro[5.5]undec-4-en-2-ylmethoxy)(tert-butyl)diphenylsilane
• 英文别名: tert-butyl-[[(2S,6S)-1,7-dioxaspiro[5.5]undec-4-en-2-yl]methoxy]-diphenylsilane
• 化学式: C₂₆H₃₄O₃Si
• 分子量: 422.64
• InChiKey: XLFUBIVUQNVTHH-NVQXNPDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1,7-dioxaspiro[5.5]undec-4-en-2-ylmethoxy)(tert-butyl)diphenylsilane 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 5.5h， 以95%的产率得到(+/-)-(2R,6R)-2-(t-butyldiphenylsilyloxymethyl)-1,7-dioxaspiro[5.5]undecane
  参考文献：
  名称：

  Au-Catalyzed Cyclization of Monopropargylic Triols: An Expedient Synthesis of Monounsaturated Spiroketals

  摘要：

  The gold-catalyzed cyclization of monopropargylic triols to form olefin-containing spiroketals is reported. The reactions are rapid and high yielding when 2 mol % of the catalyst generated in situ from Au[P(t-BU)(2)(o-biphenyI)]Cl and AgOTf is employed in THF at 0 degrees C. A range of differentially substituted triols leading to substituted 5- and 6-membered ring spiroketals were prepared and function well in the reaction.

  DOI：

  10.1021/ol802491m
• 作为产物：
  描述：

  6-(叔-丁基二甲基硅烷基氧基)-1-己炔 在 正丁基锂 、 对甲苯磺酸 、 gold(I) chloride 作用下， 以 四氢呋喃 、 正己烷 、 水 为溶剂， 反应 18.75h， 生成 (1,7-dioxaspiro[5.5]undec-4-en-2-ylmethoxy)(tert-butyl)diphenylsilane
  参考文献：
  名称：

  Controlling Regiochemistry in the Gold-Catalyzed Synthesis of Unsaturated Spiroketals

  摘要：

  A novel gold-catalyzed synthesis of unsaturated spiroketals that addresses regioselectivity issues commonly reported in metal-catalyzed spiroketalization of alkynes is reported. The reaction sequence is regulated by an acetonide protecting group which undergoes extrusion of acetone to deliver the desired spiroketals in good yields and diastereoselectivities. The reaction, which is carried out under very mild conditions employing AuCl as the catalyst, should be widely applicable in the synthesis of a broad range of spiroketals.

  DOI：

  10.1021/ol5024954

文献信息

• Au-Catalyzed Cyclization of Monopropargylic Triols: An Expedient Synthesis of Monounsaturated Spiroketals
  作者：Aaron Aponick、Chuan-Ying Li、Jean A. Palmes

  DOI：10.1021/ol802491m

  日期：2009.1.1

  The gold-catalyzed cyclization of monopropargylic triols to form olefin-containing spiroketals is reported. The reactions are rapid and high yielding when 2 mol % of the catalyst generated in situ from Au[P(t-BU)(2)(o-biphenyI)]Cl and AgOTf is employed in THF at 0 degrees C. A range of differentially substituted triols leading to substituted 5- and 6-membered ring spiroketals were prepared and function well in the reaction.
• Controlling Regiochemistry in the Gold-Catalyzed Synthesis of Unsaturated Spiroketals
  作者：Paulo H. S. Paioti、John M. Ketcham、Aaron Aponick

  DOI：10.1021/ol5024954

  日期：2014.10.17

  A novel gold-catalyzed synthesis of unsaturated spiroketals that addresses regioselectivity issues commonly reported in metal-catalyzed spiroketalization of alkynes is reported. The reaction sequence is regulated by an acetonide protecting group which undergoes extrusion of acetone to deliver the desired spiroketals in good yields and diastereoselectivities. The reaction, which is carried out under very mild conditions employing AuCl as the catalyst, should be widely applicable in the synthesis of a broad range of spiroketals.