2-propanoyl-3-phenyl-l-menthopyrazole | 155095-23-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 2-propanoyl-3-phenyl-l-menthopyrazole
• 英文别名: 1-[(4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydroindazol-2-yl]propan-1-one
• CAS: 155095-23-1
• 化学式: C₂₀H₂₆N₂O
• 分子量: 310.439
• InChiKey: AOHGDVNMRLVRON-ZBFHGGJFSA-N

物化性质

• 沸点：
  451.3±55.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  2-propanoyl-3-phenyl-l-menthopyrazole 在 丙酰氯 作用下， 生成
  参考文献：
  名称：

  一种新的手性辅助化合物的立体选择性N-酰化；3-苯基-1-薄荷脑吡唑

  摘要：

  作为具有吡唑环系统中的新的手性助剂化合物，的合成实用程序（4R，7S）-3-苯基-4-甲基-7-异丙基-4,5,6,7- tetrahydroindazole（3-苯基升-讨论了由1-薄荷酮制备的薄荷脑吡唑。

  DOI：

  10.1016/s0040-4039(00)61417-x
• 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 为溶剂， 生成 2-propanoyl-3-phenyl-l-menthopyrazole
  参考文献：
  名称：

  一种新的手性辅助化合物的立体选择性N-酰化；3-苯基-1-薄荷脑吡唑

  摘要：

  作为具有吡唑环系统中的新的手性助剂化合物，的合成实用程序（4R，7S）-3-苯基-4-甲基-7-异丙基-4,5,6,7- tetrahydroindazole（3-苯基升-讨论了由1-薄荷酮制备的薄荷脑吡唑。

  DOI：

  10.1016/s0040-4039(00)61417-x

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。
• Synthesis of optically active β-lactams by the reaction of 2-acyl-3-phenyl-<i>l</i>-menthopyrazoles with CN compounds
  作者：Choji Kashima、Kiyoshi Fukusaka、Katsumi Takahashi

  DOI：10.1002/jhet.5570340529

  日期：1997.9

  The reaction of 1-acyl-3,5-dimethylpyrazoles 1 with CN compounds was kinetically controlled with syn stereoselectivity through a lithium enolate intermediate using lithium diisopropylamide. In contrast, the anti stereoselective reaction of 1 was caused by the action of diisopropylethylamine in the presence of magnesium bromide under the thermodynamic control. Reaction of 2-acyl-3-phenyl-l-menthopyrazoles

  1-酰基-3，5-二甲基吡唑1与C N化合物的反应是通过使用二异丙基氨基化锂的烯醇锂中间体以顺式立体选择性动力学控制的。相反，在热力学控制下，在溴化镁存在下，二异丙基乙胺的作用引起1的抗立体选择性反应。观察到2-酰基-3-苯基-1-薄荷脑吡唑12与C N化合物以主要的2'S构型以较高的化学和光学产率反应。在2-丙酰基-3-苯基-1-薄荷脑吡唑（12a）与N-亚苄基-4-甲苯磺酰胺（2）。将N-酰基-吡唑和C N化合物的产物直接或以短转化步骤进一步环化成β-内酰胺。
• Resolution of secondary alcohols using 2-acyl-3-phenyl-l-menthopyrazoles as enantioselective acylating agents
  作者：Choji Kashima、Saori Mizuhara、Yohei Miwa、Yukihiro Yokoyama

  DOI：10.1016/s0957-4166(02)00472-x

  日期：2002.8

  The chelation of AlCl3 with N-acylpyrazoles leads to structural fixation of the acyl moiety and an acceleration in the rate of acylation of secondary alcohols. The chiral environment of the fixed acyl moiety of 2-acyl-3-phenyl-1-menthopyrazole 2 causes diastereofacial selectivity in the reaction with secondary alcohols, and thus 2 behaves as an enantioselective acylating agent. By the use of 2.4 molar equivalents of racemic 1-phenylethanol 3a, 2-acetyl-3-phenyl-1-menthopyrazole 2a afforded (S)-1-phenylethyl acetate (S)-4aa enantioselectively and unreacted 3a was recovered with (R)-configuration. Furthermore, the inverse configurational preferences were observed to give (R)-4aa and (S)-3a by the addition of strongly basic amines, which sometimes behaved as catalysts for enolate formation from 2 and AlCl3. These dramatic changes in stereoselective preference should be useful properties of 2-acyl-3-phenyl-1-menthopyrazole 2 as an enantioselective acylating agent. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Diastereoselective .alpha.-Alkylation of 2-Acyl-3-phenyl-l-menthopyrazoles
  作者：Choji Kashima、Iwao Fukuchi、Akira Hosomi

  DOI：10.1021/jo00104a045

  日期：1994.12

  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.
• 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.