1-[(4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydroindazol-2-yl]-3-phenylpropan-1-one | 166588-79-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-[(4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydroindazol-2-yl]-3-phenylpropan-1-one
• CAS: 166588-79-0
• 化学式: C₂₆H₃₀N₂O
• 分子量: 386.537
• InChiKey: ZCDRQFZXRYNYRD-KNQAVFIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  溴乙酸乙酯 、 1-[(4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydroindazol-2-yl]-3-phenylpropan-1-one 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以15%的产率得到ethyl 3-benzyl-4-oxo-4-(3-phenyl-l-menthopyrazol-2-yl)butanoate
  参考文献：
  名称：

  Preparation of β-Substituted γ-Keto Esters by the Grignard Reaction on N-Acylpyrazoles

  摘要：

  Various gamma -keto esters were prepared by either the alcoholysis of N-(4-oxoalkcanoyl)pyrazoles or the Grignard replacement of pyrazole moiety of 4-(N-pyrazolyl)-4-oxoalkanoic esters. By using 3-phenyl-l-menthopyrazole as a chiral auxiliary, beta -substituted gamma -keto esters were enantioselectively obtained.

  DOI：

  10.3987/com-00-s(i)37
• 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 1-[(4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydroindazol-2-yl]-3-phenylpropan-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

• Conjugate addition of grignard reagents to<i>N</i>-(α,β-unsaturated)acylpyrazoles. Diastereoselective β-alkylation using 3-phenyl-<i>l</i>-menthopyrazole
  作者：Choji Kashima、Katsumi Takahashi、Kiyoshi Fukusaka、Akira Hosomi

  DOI：10.1002/jhet.5570350303

  日期：1998.5

  The conjugate additions of N-(α,β-unsaturated)acylpyrazoles were carried out by the treatment with Grignard reagents in the presence of cuprous halides. The reaction of 2-(α,β-unsaturated)acyl-3-phenyl-l-menthopyrazoles 3a-h occurred in higher chemical yields and with asymmetric inductions on β-position, where the addition of magnesium bromide as a Lewis acid influenced to the yields and the diastereoselectivities

  通过在卤化亚铜存在下用格氏试剂处理N-（α，β-不饱和）酰基吡唑的共轭加成。2-（α，β-不饱和）酰基-3-苯基-1-薄荷基吡唑3a-h的化学收率较高，并且在β位置上具有不对称诱导作用，其中溴化镁作为路易斯酸的添加影响了收率和非对映选择性。在α-甲基化的2-（α，β-不饱和）酰基-3-苯基-1-薄荷脑吡唑3i-n中，通过非对面质子化也观察到了对α-位置的极好的不对称诱导。
• 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。
• Stereocontrolled Aldol Reaction of N-Acylpyrazoles with Aldehydes Using LDA or MgBr2-DIEA
  作者：Choji Kashima、Iwao Fukuchi、Katsumi Takahashi、Kiyoshi Fukusaka、Akira Hosomi

  DOI：10.3987/com-97-s(n)31

  日期：——

  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.
• Diastereomeric Preparation of a- and b-Phenylthio Substituted N-Acylpyrazoles
  作者：Choji Kashima、Katsumi Takahashi、Akira Hosomi

  DOI：10.3987/com-95-s14

  日期：——

  When 3-phenyl-l-menthopyrazole was used as a chiral auxiliary, the diastereomeric preparation of alpha- and beta-phenylthio-substituted N-acylpyrazoles (4 and 9) was accomplished in high yield by the alpha-sulfenylation using diphenyl disulfide and the conjugate addition of thiophenol, respectively.
• Mechanistic Insight into Catalytic Aerobic Chemoselective α-Oxidation of Acylpyrazoles
  作者：Takashi Ohshima、Ryo Yazaki、Seiya Taninokuchi

  DOI：10.3987/com-18-s(f)58

  日期：——