(3S,5S)-7-benzyloxy-5-(tert-butyldimethylsiloxy)-3-hydroxy-6,6-dimethyl-1-phenyl-1-heptanone | 224968-27-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S,5S)-7-benzyloxy-5-(tert-butyldimethylsiloxy)-3-hydroxy-6,6-dimethyl-1-phenyl-1-heptanone
• 英文别名: (3S,5S)-5-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-6,6-dimethyl-1-phenyl-7-phenylmethoxyheptan-1-one
• CAS: 224968-27-8
• 化学式: C₂₈H₄₂O₄Si
• 分子量: 470.725
• InChiKey: CHSJSUDGHKQFSC-RSXGOPAZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.64
• 重原子数：
  33
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3S,5S)-7-benzyloxy-5-(tert-butyldimethylsiloxy)-3-hydroxy-6,6-dimethyl-1-phenyl-1-heptanone 在 lithium aluminium tetrahydride 、 双(三甲基硅基)过氧化物 、 racemic trans-N,N'-bis(p-toluenesulfonyl)cyclohexane-1,2-diamine 、 4 A molecular sieve 、 camphor-10-sulfonic acid 、 四氯化锡 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 7.5h， 生成 2-<(4R,6S)-6-(2-benzyloxy-1,1-dimethylethyl)-2,2-dimethyl-1,3-dioxan-4-yl>ethanol
  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
• 作为产物：
  描述：

  (S)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-pentanoic acid phenyl ester 在 LaLi₃ tris((S)-binaphthoxide) 、 Celite 、 水 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 30.5h， 生成 (3S,5S)-7-benzyloxy-5-(tert-butyldimethylsiloxy)-3-hydroxy-6,6-dimethyl-1-phenyl-1-heptanone
  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

文献信息

• Direct Catalytic Asymmetric Aldol Reaction
  作者：Naoki Yoshikawa、Yoichi M. A. Yamada、Jagattaran Das、Hiroaki Sasai、Masakatsu Shibasaki

  DOI：10.1021/ja990031y

  日期：1999.5.1

  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.