3-methyl-1-[(4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydroindazol-2-yl]butan-1-one | 166588-78-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 3-methyl-1-[(4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydroindazol-2-yl]butan-1-one
• CAS: 166588-78-9
• 化学式: C₂₂H₃₀N₂O
• 分子量: 338.493
• InChiKey: AMTIZNUYLGDOOY-AEFFLSMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  34.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苯甲醛 、 3-methyl-1-[(4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydroindazol-2-yl]butan-1-one 在 N,N-二异丙基乙胺 、 magnesium bromide 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 (S)-2-((S)-Hydroxy-phenyl-methyl)-1-((4R,7S)-7-isopropyl-4-methyl-3-phenyl-4,5,6,7-tetrahydro-indazol-2-yl)-3-methyl-butan-1-one 、 (S)-2-((R)-Hydroxy-phenyl-methyl)-1-((4R,7S)-7-isopropyl-4-methyl-3-phenyl-4,5,6,7-tetrahydro-indazol-2-yl)-3-methyl-butan-1-one
  参考文献：
  名称：

  Stereocontrolled Aldol Reaction of N-Acylpyrazoles with Aldehydes Using LDA or MgBr2-DIEA

  摘要：

  The aldol reaction of 1-acyl-3,5-dimethylpyrazoles (1) was kinetically controlled with syn stereoselectivity through lithium enolate intermediate using LDA. On the contrary, the anti stereoselective aldol reaction of 1 was caused by the action of DIEA in the presence of MgBr2 under the thermodynamic control. in the formation of syn-aldol products using 3-phenyl-1-menthopyrazole as a chiral auxiliary, the diastereoselectivity was observed up to 81% de with the predominant configuration of 2'S form.

  DOI：

  10.3987/com-97-s(n)31
• 作为产物：
  描述：

  (-)-薄荷酮 在 盐酸 、 一水合肼 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 苯 为溶剂， 反应 21.0h， 生成 3-methyl-1-[(4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydroindazol-2-yl]butan-1-one
  参考文献：
  名称：

  Diastereoselective .alpha.-Alkylation of 2-Acyl-3-phenyl-l-menthopyrazoles

  摘要：

  N-Acylpyrazoles were alpha-alkylated in good yields by the treatment with alkyl halides after metalation with LDA or LiHMDS, In the case of chiral N-acylpyrazoles, e.g., 2-acyl-3-phenyl-l-menthopyrazoles (4), the alpha-alkylation was highly diastereoselective. The subsequent alpha-alkylation products could be converted into esters in good yield in the presence of BF3.OEt(2) without the loss of the optical purity.

  DOI：

  10.1021/jo00104a045

文献信息

• Enantiomerically enriched preparation of enolizable β-keto amides. Diastereoselective α-acylation and subsequent aminolysis of 2-acyl-3-phenyl-l-menthopyrazoles
  作者：Choji Kashima、Iwao Fukuchi、Katsumi Takahashi、Akira Hosomi

  DOI：10.1016/0040-4020(96)00550-9

  日期：1996.7

  After deprotonation with LDA, 2-acyl-3-phenyl-l-menthopyrazoles (13) were diastereomerically α-acylated to give N-(3-phenyl-l-menthopyrazolyl) β-keto amides (14–19). The subsequent amides were converted into the corresponding N-alkyl amides (21–24) retaining their enantiomeric enrichment on the α-position. These are the first examples of enolizable β-keto acid derivatives having only one chiral center

  用LDA去质子化后，2-酰基-3-苯基-升-menthopyrazoles（13）的非对映体α -酰化，得到N-（3-苯基升-menthopyrazolyl）β酮酰胺（14-19）。随后的酰胺被转化为相应的N-烷基酰胺（21-24），使它们的对映体富集在α位。这些是在α位仅具有一个手性中心的可烯醇化的β-酮酸衍生物的第一个实例。这些手性β-酮酰胺在干燥的苯中出奇地稳定，并且它们的光学不对称性在室温下几乎保留了两周而没有任何差向异构化。