(1R,2R,5S)-6,6-Di-tert-butyl-2-((S)-1-triisopropylsilanyloxy-propyl)-6-sila-bicyclo[3.1.0]hexane

• 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: (1R,2R,5S)-6,6-Di-tert-butyl-2-((S)-1-triisopropylsilanyloxy-propyl)-6-sila-bicyclo[3.1.0]hexane
• 英文别名: [(1S)-1-[(1R,2R,5S)-6,6-ditert-butyl-6-silabicyclo[3.1.0]hexan-2-yl]propoxy]-tri(propan-2-yl)silane
• 化学式: C₂₅H₅₂OSi₂
• 分子量: 424.858
• InChiKey: BPNXPVQNHRJYFW-WZYRSQIMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.17
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R,2R,5S)-6,6-Di-tert-butyl-2-((S)-1-triisopropylsilanyloxy-propyl)-6-sila-bicyclo[3.1.0]hexane 在 copper(l) iodide copper(II) sulfate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 31.0h， 生成 (3aR,4R,6aR)-1,1-Di-tert-butyl-4-((R)-1-triisopropylsilanyloxy-propyl)-hexahydro-cyclopenta[c][1,2]oxasilol-3-ol
  参考文献：
  名称：

  Diastereoselective Silacyclopropanations of Functionalized Chiral Alkenes

  摘要：

  Lithium reduction of di-tert-butyldichlorosilane and thermal silylene transfer (105-125 degrees C) are complementary methods for the highly diastereoselective silacyclopropanations of a range of functionalized chiral olefins to afford complex silacycles. We have shown that functionalized cyclohexenes, cyclopentenes, norbornenes, and 1,1-disubstituted alkenes undergo silacyclopropanation with excellent diastereoselectivity (92:8 to >99:1). Our results demonstrate that steric interactions, rather than oxygen-directing effects, control the approach of the silylene or silylenoid intermediate to the olefin. We believe that the sterically demanding nature of the di-tert-butylsilylene species prevents coordination to the oxygen functionality. Thermal silylene transfer conditions exhibit broad functional group tolerance; the elevated temperatures for silylene transfer, however, cannot be employed for the silacyclopropanation of substituted cyclohexenes and 1,1-disubstituted alkenes. Elaboration of the resulting functionalized silacyclopropanes provides an efficient route to polyoxygenated products.

  DOI：

  10.1021/ja020183k
• 作为产物：
  描述：

  二叔丁基氯硅烷 在 lithium 作用下， 以 四氢呋喃 、 正己烷 、 氘代苯 为溶剂， 反应 64.0h， 生成 (1R,2R,5S)-6,6-Di-tert-butyl-2-((S)-1-triisopropylsilanyloxy-propyl)-6-sila-bicyclo[3.1.0]hexane
  参考文献：
  名称：

  Diastereoselective Silacyclopropanations of Functionalized Chiral Alkenes

  摘要：

  Lithium reduction of di-tert-butyldichlorosilane and thermal silylene transfer (105-125 degrees C) are complementary methods for the highly diastereoselective silacyclopropanations of a range of functionalized chiral olefins to afford complex silacycles. We have shown that functionalized cyclohexenes, cyclopentenes, norbornenes, and 1,1-disubstituted alkenes undergo silacyclopropanation with excellent diastereoselectivity (92:8 to >99:1). Our results demonstrate that steric interactions, rather than oxygen-directing effects, control the approach of the silylene or silylenoid intermediate to the olefin. We believe that the sterically demanding nature of the di-tert-butylsilylene species prevents coordination to the oxygen functionality. Thermal silylene transfer conditions exhibit broad functional group tolerance; the elevated temperatures for silylene transfer, however, cannot be employed for the silacyclopropanation of substituted cyclohexenes and 1,1-disubstituted alkenes. Elaboration of the resulting functionalized silacyclopropanes provides an efficient route to polyoxygenated products.

  DOI：

  10.1021/ja020183k

文献信息

• Diastereoselective Silacyclopropanations of Functionalized Chiral Alkenes
  作者：Tom G. Driver、Annaliese K. Franz、K. A. Woerpel

  DOI：10.1021/ja020183k

  日期：2002.6.1

  Lithium reduction of di-tert-butyldichlorosilane and thermal silylene transfer (105-125 degrees C) are complementary methods for the highly diastereoselective silacyclopropanations of a range of functionalized chiral olefins to afford complex silacycles. We have shown that functionalized cyclohexenes, cyclopentenes, norbornenes, and 1,1-disubstituted alkenes undergo silacyclopropanation with excellent diastereoselectivity (92:8 to >99:1). Our results demonstrate that steric interactions, rather than oxygen-directing effects, control the approach of the silylene or silylenoid intermediate to the olefin. We believe that the sterically demanding nature of the di-tert-butylsilylene species prevents coordination to the oxygen functionality. Thermal silylene transfer conditions exhibit broad functional group tolerance; the elevated temperatures for silylene transfer, however, cannot be employed for the silacyclopropanation of substituted cyclohexenes and 1,1-disubstituted alkenes. Elaboration of the resulting functionalized silacyclopropanes provides an efficient route to polyoxygenated products.