6-[tert-butyl(dimethyl)silyl]oxy-2,2,5-trimethylhexan-3-one | 130537-59-6

• 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: 6-[tert-butyl(dimethyl)silyl]oxy-2,2,5-trimethylhexan-3-one
• CAS: 130537-59-6
• 化学式: C₁₅H₃₂O₂Si
• 分子量: 272.503
• InChiKey: ODHLHFGJQGLLJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.65
• 重原子数：
  18.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  6-[tert-butyl(dimethyl)silyl]oxy-2,2,5-trimethylhexan-3-one 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成
  参考文献：
  名称：

  1,3-Allylic Strain as a Control Element in the Paternò−Büchi Reaction of Chiral Silyl Enol Ethers:  Synthesis of Diastereomerically Pure Oxetanes Containing Four Contiguous Stereogenic Centers

  摘要：

  The facial diastereoselectivity in the Patemo-Buchi reaction of chiral silyl enol ethers and benzaldehyde was studied. The substituents (R(S), R(L)) at the stereogenic carbon atom (-C*HR(S)R(L)) attached to the beta-position of the silyl enol ether were varied in order to evaluate the influence of steric bulk and electronic effects. The combined yields for the two diastereomeric 3-(silyloxy)oxetanes a and b. range between 44% and 76%. In accordance with the 1,3-allylic strain model the facial diastereoselectivity (diastereomeric ratio (dr) = alb) was best with large(R(L) = t-Bu, SiMe(2)Ph) and polar (R(L) = OMe) substituents at the gamma-position of the silyl enol ether (dr up to >95/5). Two regioselective ring opening reactions were applied to the product oxetanes 29a, 50, and 51. They furnished diastereomerically pure diols (52, 53) and triols (31) in excellent yields.

  DOI：

  10.1021/ja963827v
• 作为产物：
  描述：

  叔丁基二甲基(2-丙炔氧基)硅烷 在 palladium dihydroxide 正丁基锂 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 生成 6-[tert-butyl(dimethyl)silyl]oxy-2,2,5-trimethylhexan-3-one
  参考文献：
  名称：

  1,3-Allylic Strain as a Control Element in the Paternò−Büchi Reaction of Chiral Silyl Enol Ethers:  Synthesis of Diastereomerically Pure Oxetanes Containing Four Contiguous Stereogenic Centers

  摘要：

  The facial diastereoselectivity in the Patemo-Buchi reaction of chiral silyl enol ethers and benzaldehyde was studied. The substituents (R(S), R(L)) at the stereogenic carbon atom (-C*HR(S)R(L)) attached to the beta-position of the silyl enol ether were varied in order to evaluate the influence of steric bulk and electronic effects. The combined yields for the two diastereomeric 3-(silyloxy)oxetanes a and b. range between 44% and 76%. In accordance with the 1,3-allylic strain model the facial diastereoselectivity (diastereomeric ratio (dr) = alb) was best with large(R(L) = t-Bu, SiMe(2)Ph) and polar (R(L) = OMe) substituents at the gamma-position of the silyl enol ether (dr up to >95/5). Two regioselective ring opening reactions were applied to the product oxetanes 29a, 50, and 51. They furnished diastereomerically pure diols (52, 53) and triols (31) in excellent yields.

  DOI：

  10.1021/ja963827v

文献信息

• The diastereoselective influences of remote substituents on enolate alkylations
  作者：Glenn J. McGarvey、Marc W. Andersen

  DOI：10.1016/s0040-4039(00)97678-0

  日期：1990.1

  The methylation of a series of γ-oxygenated ketones enolates (3) has been examined with the result that poor to outstanding levels of diastereoselectivity are observed that appear to be predictably consistent with a general model for asymmetric electrophilic addition reactions.

  已经检查了一系列γ-氧化酮烯醇化物（3）的甲基化，结果观察到较差至优异的非对映选择性水平，这似乎与非对称亲电加成反应的一般模型可预测地一致。