(S)-1,2-dihydroxy-5,5-dimethyl-1,2-O-isopropylidene-4-hexanone | 187811-55-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-1,2-dihydroxy-5,5-dimethyl-1,2-O-isopropylidene-4-hexanone
• 英文别名: 1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3,3-dimethylbutan-2-one
• CAS: 187811-55-8
• 化学式: C₁₁H₂₀O₃
• 分子量: 200.278
• InChiKey: CCLNOQACOUGLDR-QMMMGPOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.14
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-1,2-dihydroxy-5,5-dimethyl-1,2-O-isopropylidene-4-hexanone 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成 4-(2,2-dimethyl-1,3-dioxolan-4-yl)-3-(1,1-dimethylethyl)-2-phenyl-3-[(trimethylsilyl)oxy]oxetane
  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：

  1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3,3-dimethylbutan-2-ol 在 四丙基高钌酸铵 4 A molecular sieve 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以82%的产率得到(S)-1,2-dihydroxy-5,5-dimethyl-1,2-O-isopropylidene-4-hexanone
  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