(Z)-(2'S,3'R,4'R,5'R,6'R)-2-[2'(3',4',5',6'-Di-O-isopropylidene)tetrahydropyranyl]-1-methoxy-1-phenylthio ethene | 245122-07-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: (Z)-(2'S,3'R,4'R,5'R,6'R)-2-[2'(3',4',5',6'-Di-O-isopropylidene)tetrahydropyranyl]-1-methoxy-1-phenylthio ethene
• CAS: 245122-07-0
• 化学式: C₂₀H₂₆O₆S
• 分子量: 394.489
• InChiKey: ZUQLGYLCVAEWRU-XUUFNDLWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.66
• 重原子数：
  27.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  55.38
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (Z)-(2'S,3'R,4'R,5'R,6'R)-2-[2'(3',4',5',6'-Di-O-isopropylidene)tetrahydropyranyl]-1-methoxy-1-phenylthio ethene 在 Hydroquinone 1,4-phthalazinediyl diether 、 甲基磺酰胺 、 α-AD mix {K4[Fe(CN)6], OsO4, Na2CO3, (DHQ)2-PHAL} 、 水 、 sodium sulfite 作用下， 以 水 、 叔丁醇 为溶剂， 反应 0.75h， 生成 (2S,2'S,3'R,4'R,5'R,6'R)-2-Hydroxy-2-[2'(3',4',5',6'-di-O-isopropylidene)tetrahydropyranyl]acetic acid methyl ester 、 (2R,2'S,3'R,4'R,5'R,6'R)-2-Hydroxy-2-[2'(3',4',5',6'-di-O-isopropylidene)tetrahydropyranyl]acetic acid methyl ester
  参考文献：
  名称：

  Asymmetric Nucleophilic Acylation of Aldehydes via 1,1-Heterodisubstituted Alkenes

  摘要：

  Aldehydes are asymmetrically acylated by a two step sequence that is initiated by a homologation step to 1,1-heterodisubstituted alkenes followed by asymmetric dihydroxylation. Thus, ketene O,S-acetals are efficiently prepared from aldehydes by a Peterson olefination with lithiated methoxy-phenylthiotrimethylsilyl methane 14 as the C-1 source. Although they are dihydroxylated with the Sharpless catalyst with moderate to good enantioselectivity (62-80% ee), the process is not efficient owing to the low chemical yields of the desired alpha-hydroxy methyl esters (7-37%). Use of the corresponding sulfoxide 24 or sulfon 25 led to an improved chemical yield of alpha-hydroxy methyl ester 19, but the stereoselectivity was diminished. In contrast, intermediate ketene O,O-acetals are prepared by a Horner-Wittig reaction with phosphine oxide 31 and are dihydroxylated both with good chemical and stereochemical yield. The concept is applicable to aromatic, aliphatic, and chiral aldehydes. For example, this short sequence allows exclusive and independent preparation of both diastereomeric heptoses 69a and 69b.

  DOI：

  10.1002/(sici)1521-3765(19990802)5:8<2270::aid-chem2270>3.0.co;2-l
• 作为产物：
  描述：

  双丙酮半乳糖 在 Phenanthroline 、 四甲基乙二胺 、 仲丁基锂 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 2.5h， 生成 (Z)-(2'S,3'R,4'R,5'R,6'R)-2-[2'(3',4',5',6'-Di-O-isopropylidene)tetrahydropyranyl]-1-methoxy-1-phenylthio ethene
  参考文献：
  名称：

  Asymmetric Nucleophilic Acylation of Aldehydes via 1,1-Heterodisubstituted Alkenes

  摘要：

  Aldehydes are asymmetrically acylated by a two step sequence that is initiated by a homologation step to 1,1-heterodisubstituted alkenes followed by asymmetric dihydroxylation. Thus, ketene O,S-acetals are efficiently prepared from aldehydes by a Peterson olefination with lithiated methoxy-phenylthiotrimethylsilyl methane 14 as the C-1 source. Although they are dihydroxylated with the Sharpless catalyst with moderate to good enantioselectivity (62-80% ee), the process is not efficient owing to the low chemical yields of the desired alpha-hydroxy methyl esters (7-37%). Use of the corresponding sulfoxide 24 or sulfon 25 led to an improved chemical yield of alpha-hydroxy methyl ester 19, but the stereoselectivity was diminished. In contrast, intermediate ketene O,O-acetals are prepared by a Horner-Wittig reaction with phosphine oxide 31 and are dihydroxylated both with good chemical and stereochemical yield. The concept is applicable to aromatic, aliphatic, and chiral aldehydes. For example, this short sequence allows exclusive and independent preparation of both diastereomeric heptoses 69a and 69b.

  DOI：

  10.1002/(sici)1521-3765(19990802)5:8<2270::aid-chem2270>3.0.co;2-l