(-)-(1R,2R,4S)-1-hydroxy-1-phenyl-2,5,5-trimethyl-4-<(trimethylsilyl)oxy>-3-hexanone | 131614-05-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (-)-(1R,2R,4S)-1-hydroxy-1-phenyl-2,5,5-trimethyl-4-<(trimethylsilyl)oxy>-3-hexanone
• 英文别名: (-)-(1R,2R,4S)-1-hydroxy-1-phenyl-2,5,5-trimethyl-4-[(trimethylsilyl)oxy]-3-hexanone；rel-(1R,2R,4S)-1-Hydroxy-2,5,5-trimethyl-1-phenyl-4-[(trimethylsilyl)oxy]-3-hexanone；(1R,2R,4S)-1-hydroxy-2,5,5-trimethyl-1-phenyl-4-trimethylsilyloxyhexan-3-one
• CAS: 131614-05-6
• 化学式: C₁₈H₃₀O₃Si
• 分子量: 322.52
• InChiKey: MFWIMSWYMSQWCC-FRFSOERESA-N

物化性质

• 沸点：
  382.3±32.0 °C(Predicted)
• 密度：
  0.990±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.19
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 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：

  (-)-(1R,2R,4S)-1-hydroxy-1-phenyl-2,5,5-trimethyl-4-<(trimethylsilyl)oxy>-3-hexanone 在 盐酸 作用下， 以 甲醇 为溶剂， 生成 (1R,2R,4S)-1,4-dihydroxy-2,5,5-trimethyl-1-phenyl-3-hexanone
  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 (-)-(1R,2R,4S)-1-hydroxy-1-phenyl-2,5,5-trimethyl-4-<(trimethylsilyl)oxy>-3-hexanone
  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

• PANYACHOTIPUN, CHITCHANUN;THORNTON, EDWARD R., TETRAHEDRON LETT., 31,(1990) N2, C. 6001-6004
  作者：PANYACHOTIPUN, CHITCHANUN、THORNTON, EDWARD R.

  DOI：——

  日期：——
• 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：——