(-)-(3S,5S,6R)-6-hydroxy-2,2,5,7-tetramethyl-3-<(trimethylsilyl)oxy>-4-octanone | 133006-34-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(3S,5S,6R)-6-hydroxy-2,2,5,7-tetramethyl-3-<(trimethylsilyl)oxy>-4-octanone
• 英文别名: (-)-(3S,5S,6R)-6-hydroxy-2,2,5,7-tetramethyl-3-[(trimethylsilyl)oxy]-4-octanone；(3S,5S,6R)-6-hydroxy-2,2,5,7-tetramethyl-3-trimethylsilyloxyoctan-4-one
• CAS: 133006-34-5
• 化学式: C₁₅H₃₂O₃Si
• 分子量: 288.503
• InChiKey: BEPJMOHQMMVGEL-OUCADQQQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  (-)-(3S,5S,6R)-6-hydroxy-2,2,5,7-tetramethyl-3-<(trimethylsilyl)oxy>-4-octanone 在 盐酸 作用下， 以 甲醇 为溶剂， 生成 (3S,5S,6R)-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
• 作为产物：
  描述：

  (S)-(-)-2-羟基-3,3-二甲基丁酸 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 (-)-(3S,5S,6R)-6-hydroxy-2,2,5,7-tetramethyl-3-<(trimethylsilyl)oxy>-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

• Acyclic stereoselection. 6. A reagent for achieving high 1,2-diastereoselection in the aldol conversion of chiral aldehydes into 3-hydroxy-2-methylcarboxylic acids
  作者：Clayton H. Heathcock、Michael C. Pirrung、Charles T. Buse、James P. Hagen、Steven D. Young、John E. Sohn

  DOI：10.1021/ja00517a056

  日期：1979.11
• Acyclic stereoselection. 35. Effect of cation on diastereofacial selectivity in aldol reactions of a chiral α-silyloxy ketone.
  作者：Clayton H Heathcock、Simeon Arseniyadis

  DOI：10.1016/s0040-4039(00)95111-6

  日期：1985.1
• 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：——
• HEATHCOCK, C. H.;ARSENIYADIS, S., TETRAHEDRON LETT., 1985, 26, N 49, 6009-6012
  作者：HEATHCOCK, C. H.、ARSENIYADIS, S.

  DOI：——

  日期：——