(S)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-pentan-1-ol | 224968-25-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-pentan-1-ol
• CAS: 224968-25-6
• 化学式: C₂₀H₃₆O₃Si
• 分子量: 352.59
• InChiKey: UZNOMPSOHSCIGZ-SFHVURJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.0
• 重原子数：
  24.0
• 可旋转键数：
  9.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-pentan-1-ol 在 4-二甲氨基吡啶 、 碳酸氢钠 、 三乙胺 、 N,N-二异丙基乙胺 、 三苯基膦 、 sodium iodide 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 24.0h， 生成 2-((E)-4-{(4S,5S)-5-[(Z)-(S)-6-Benzyloxy-4-(tert-butyl-dimethyl-silanyloxy)-5,5-dimethyl-hex-1-enyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-but-3-en-1-ynyl)-oxazole-4-carboxylic acid ethyl ester
  参考文献：
  名称：

  合成对二唑的研究：合成一个被屏蔽的二甲苯基D 1的北半部和一个被屏蔽的二甲苯基A 1的北半部的环丙烷类似物

  摘要：

  描述了天然产物二异恶唑D 1的被掩蔽的北半部和二异恶唑A 1的被掩蔽的北半部的环丙烷类似物的合成。在这两种情况下，合成都涉及Z选择性Wittig烯烃化和Sonogashira交叉偶联反应作为关键步骤。

  DOI：

  10.1016/s0040-4020(03)00916-5
• 作为产物：
  描述：

  (S)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-pentanoic acid phenyl ester 在 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以300 mg的产率得到(S)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-pentan-1-ol
  参考文献：
  名称：

  Direct Catalytic Asymmetric Aldol Reaction

  摘要：

  The direct catalytic asymmetric aldol reaction using aldehydes and unmodified ketones is described for the first time herein. This reaction was first found to be promoted by 20 mol % of anhydrous (R)-LLB (L = lanthanum, L = lithium, B = (R)-binaphthol moiety) at -20 OC, giving a variety of aldol products in ee's ranging from 44 to 94%. This asymmetric reaction has been greatly improved by developing a new heteropolymetallic asymmetric catalyst [(R)-LLB, KOH, and H2O]. Using 3-8 mol % of this catalyst, a variety of direct catalytic asymmetric aldol reactions were again found to proceed smoothly, affording aldol products in ee's ranging from 30 to 93% and in good to excellent yields. Interestingly, the use of this new heteropolymetallic asymmetric catalyst has realized a diastereoselective and enantioselective aldol reaction using cyclopentanone for the first time. It is also noteworthy that a variety of aldehydes, including hexanal, can be utilized for the current direct catalytic asymmetric aldol reaction. Chiral aldehydes containing alpha-hydrogen including (S)-hydrocinnamaldehyde-alpha-d have been found to produce the corresponding aldol products with negligible racemization (0-4%) at the a-position One of the aldol products has been successfully converted to the key synthetic intermediates of epothilone A and bryostatin 7. The possible structure of the heteropolymetallic catalyst is also discussed. Finally, mechanistic studies have revealed a characteristic reaction pathway, namely that the reaction is kinetically controlled and the rate-determining step is the deprotonation of the ketone. This is consistent with the fact that the reaction rate is independent of the concentration of the aldehyde.

  DOI：

  10.1021/ja990031y