(3S,5S,6S)-3,6-dihydroxy-2,2,5,7-tetramethyl-4-octanone | 133006-44-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (3S,5S,6S)-3,6-dihydroxy-2,2,5,7-tetramethyl-4-octanone
• 英文别名: (3S,5R,6R)-3,6-dihydroxy-2,2,5,7-tetramethyloctan-4-one
• CAS: 133006-44-7
• 化学式: C₁₂H₂₄O₃
• 分子量: 216.321
• InChiKey: IPSGGQRZSUXYPJ-FXPVBKGRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.62
• 重原子数：
  15.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  57.53
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (3S,5S,6S)-3,6-dihydroxy-2,2,5,7-tetramethyl-4-octanone 在 sodium periodate 作用下， 以 甲醇 、 水 为溶剂， 生成 (2SR,3SR)-2,4-dimethyl-3-hydroxypentanoic acid
  参考文献：
  名称：

  Protocols for the preparation of each of the four possible stereoisomeric .alpha.-alkyl-.beta.-hydroxy carboxylic acids from a single chiral aldol reagent

  摘要：

  Protocols have been devised whereby all four possible stereoisomeric alpha-alkyl-beta-hydroxy carboxylic acids can be derived from a single aldol reagent, hydroxy ketone 3. Compound 3, obtained in enantiomerically homogeneous form in 50% overall yield from tert-butylglycine (1), is used for aldol reactions in the form of its trimethylsilyl and tert-butyldimethylsilyl derivatives, 4 and 5. The Z lithium and Z boron enolates of 4 react with various aldehydes to give aldols 8 and 9, respectively. Deprotonation of 4 by bromomagnesium 2,2,6,6-tetramethylpiperidide (MTMP) gives the E enolate, which may be trapped by trimethylsilyl chloride to obtain the E silyl enol ether 11. The E bromomagnesium enolate of 4 reacts with aldehydes to give aldols of structure 15. Transmetalation of the bromomagnesium enolate of keto ether 5 is accomplished by reaction with (triisopropoxy)titanium chloride. The resulting E (triisopropoxy)titanium enolate reacts with aldehydes to provide aldols of structure 17. The aldols resulting from the foregoing reactions are hydrolyzed to keto diols 19-22, which are oxidized to the stereoisomeric alpha-methyl-beta-hydroxy carboxylic acids 23-26.

  DOI：

  10.1021/jo00007a043
• 作为产物：
  描述：

  (S)-(-)-2-羟基-3,3-二甲基丁酸 在 2,2,6,6-四甲基哌啶 、 盐酸 、 乙基溴化镁 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 30.5h， 生成 (3S,5S,6S)-3,6-dihydroxy-2,2,5,7-tetramethyl-4-octanone
  参考文献：
  名称：

  Protocols for the preparation of each of the four possible stereoisomeric .alpha.-alkyl-.beta.-hydroxy carboxylic acids from a single chiral aldol reagent

  摘要：

  Protocols have been devised whereby all four possible stereoisomeric alpha-alkyl-beta-hydroxy carboxylic acids can be derived from a single aldol reagent, hydroxy ketone 3. Compound 3, obtained in enantiomerically homogeneous form in 50% overall yield from tert-butylglycine (1), is used for aldol reactions in the form of its trimethylsilyl and tert-butyldimethylsilyl derivatives, 4 and 5. The Z lithium and Z boron enolates of 4 react with various aldehydes to give aldols 8 and 9, respectively. Deprotonation of 4 by bromomagnesium 2,2,6,6-tetramethylpiperidide (MTMP) gives the E enolate, which may be trapped by trimethylsilyl chloride to obtain the E silyl enol ether 11. The E bromomagnesium enolate of 4 reacts with aldehydes to give aldols of structure 15. Transmetalation of the bromomagnesium enolate of keto ether 5 is accomplished by reaction with (triisopropoxy)titanium chloride. The resulting E (triisopropoxy)titanium enolate reacts with aldehydes to provide aldols of structure 17. The aldols resulting from the foregoing reactions are hydrolyzed to keto diols 19-22, which are oxidized to the stereoisomeric alpha-methyl-beta-hydroxy carboxylic acids 23-26.

  DOI：

  10.1021/jo00007a043

文献信息

• VAN, DRAANEN NANINE A.;ARSENIYADIS, SIMEON;CRIMMINS, MICHAEL T.;HEATHCOCK+, J. ORG. CHEM., 56,(1991) N, C. 2499-2506
  作者：VAN, DRAANEN NANINE A.、ARSENIYADIS, SIMEON、CRIMMINS, MICHAEL T.、HEATHCOCK+

  DOI：——

  日期：——