(S)-5-Benzyloxy-3-hydroxy-4,4-dimethyl-1-phenyl-pentan-1-one | 212050-32-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-5-Benzyloxy-3-hydroxy-4,4-dimethyl-1-phenyl-pentan-1-one
• 英文别名: (3S)-3-hydroxy-4,4-dimethyl-1-phenyl-5-phenylmethoxypentan-1-one
• CAS: 212050-32-3
• 化学式: C₂₀H₂₄O₃
• 分子量: 312.409
• InChiKey: UEPHVINVUVWYHN-IBGZPJMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-5-Benzyloxy-3-hydroxy-4,4-dimethyl-1-phenyl-pentan-1-one 在 sodium dihydrogenphosphate 、 lithium aluminium tetrahydride 、 双(三甲基硅基)过氧化物 、 LaLi₃ tris((S)-binaphthoxide) 、 racemic trans-N,N'-bis(p-toluenesulfonyl)cyclohexane-1,2-diamine 、 4 A molecular sieve 、 Celite 、 camphor-10-sulfonic acid 、 水 、 四氯化锡 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 氟化氢吡啶 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 88.75h， 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：

  3-benzyloxypivalic aldehyde 、 苯乙酮 在 barium isopropoxide 、 (R)-2-羟基-2’-甲氧基-1,1’-联萘 作用下， 以 乙二醇二甲醚 为溶剂， 反应 48.0h， 生成 (S)-5-Benzyloxy-3-hydroxy-4,4-dimethyl-1-phenyl-pentan-1-one
  参考文献：
  名称：

  新型钡配合物促进的直接催化不对称醛醇缩合反应

  摘要：

  已经实现了由不对称钡络合物促进的醛和未改性酮的直接催化不对称醛醇缩合反应。钡催化剂BaB-M的可能结构具有路易斯酸和布朗斯台德碱的功能，通过LDI-TOFMS，13 C-NMR光谱和对反应条件的广泛研究来表征。

  DOI：

  10.1016/s0040-4039(98)01120-4

文献信息

• Catalytic asymmetric aldol reaction of ketones and aldehydes using chiral calcium alkoxides
  作者：Takeyuki Suzuki、Noriyuki Yamagiwa、Yoshimi Matsuo、Shigeru Sakamoto、Kentaro Yamaguchi、Masakatsu Shibasaki、Ryoji Noyori

  DOI：10.1016/s0040-4039(01)00819-x

  日期：2001.7

  A chiral hydrobenzoin/Ca complex catalyzes the reaction of acetophenone and aliphatic aldehydes to give the corresponding aldol products in up to 91% ee.

  手性氢安息香/ Ca复合物催化苯乙酮与脂族醛的反应，得到相应的羟醛产物，其ee含量高达91％。
• 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.
• Direct catalytic asymmetric aldol reactions promoted by a novel barium complex
  作者：Yoichi M.A. Yamada、Masakatsu Shibasaki

  DOI：10.1016/s0040-4039(98)01120-4

  日期：1998.7

  A direct catalytic asymmetric aldol reaction of an aldehyde and an unmodified ketone promoted by an asymmetric barium complex has been achieved. The possible structure of the barium catalyst, BaB-M, which possesses the function of a Lewis acid and a Brønsted base, was characterized by LDI-TOFMS, 13C-NMR spectroscopy and extensive studies of reaction conditions.

  已经实现了由不对称钡络合物促进的醛和未改性酮的直接催化不对称醛醇缩合反应。钡催化剂BaB-M的可能结构具有路易斯酸和布朗斯台德碱的功能，通过LDI-TOFMS，13 C-NMR光谱和对反应条件的广泛研究来表征。