3-苯基-l-薄荷吡唑 | 155095-10-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 3-苯基-l-薄荷吡唑
• 中文别名: 1H-吲唑,4,5,6,7-四氢-4-甲基-7-(1-甲基乙基)-3-苯基-,(4R,7S)-
• 英文名称: 3-phenyl-l-menthopyrazole
• 英文别名: (4R,7S)-4-methyl-3-phenyl-7-propan-2-yl-4,5,6,7-tetrahydro-1H-indazole
• CAS: 155095-10-6
• 化学式: C₁₇H₂₂N₂
• 分子量: 254.375
• InChiKey: CLTINXZUQWHNMS-OCCSQVGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  28.7
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-苯基-l-薄荷吡唑 在 三乙胺 、 (2S,4S,5R)-1-(anthracen-9-ylmethyl)-5-ethenyl-2-[(R)-(prop-2-en-1-yloxy)(quinolin-4-yl)methyl]-1-azabicyclo[2.2.2]octan-1-ium bromide 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 38.0h， 生成 (4R,7S)-1-[{(2'S)-(1'-benzyloxycarbonyl)aziridin-2'-yl}carbonyl]-7-isopropyl-4-methyl-3-phenyl-4,5,6,7-tetrahydro-1H-indazole
  参考文献：
  名称：

  Diastereoselective Aziridination of Chiral Electron-Deficient Olefins with N-Chloro-N-sodiocarbamates Catalyzed by Chiral Quaternary Ammonium Salts

  摘要：

  Chiral quaternary ammonium salt-catalyzed diastereoselective aziridination of electron-deficient olefins that possess a chiral auxiliary with N-chloro-N-sodiocarbamates was developed. The key to high stereoselectivity was found to be the employment of the "matching" stereochemical combination of chiral auxiliary/ammonium salt. For example, when 3-phenyl-(4R,7S)-4-methyl-7-isopropyl-4,S,6,7-tetrahydroindazole (L-menthopyrazole) as a chiral auxiliary and a cinchonidine-derived chiral ammonium salt as a catalyst were applied to the reaction system, perfect diastereoselectivity was realized. Furthermore, the preparation of enantiomerically pure aziridines by removal of the chiral auxiliary was demonstrated.

  DOI：

  10.1021/jo2010632
• 作为产物：
  描述：

  (-)-薄荷酮 在 盐酸 、 一水合肼 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 3-苯基-l-薄荷吡唑
  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

• Asymmetric reaction of diethylzinc with aldehydes catalyzed by <i>l</i> ‐menthopyrazole derivatives
  作者：Choji Kashima、Kohei Higashide、Yohei Miwa、Yoshihiro Tsukamoto

  DOI：10.1002/jhet.5570390511

  日期：2002.9

  N-Hydroxyalkyl-1-menthopyrazoles acted as a chiral catalyst for the diethylzinc (1) addition to aromatic aldehydes, and 1-aryl-1-propanols were afforded enantioselectively. These reactions were carried out optimally in toluene at 40 °C in the presence of 30 mol% of (2′S)-2-(2-phenyl-2-hydroxyethyl)-3-phenyl-1-men-thopyrazole ((S)-16d) to afford optically active 1-aryl-1-propanols up to 70% ee (S).

  Ñ -Hydroxyalkyl- 1 -menthopyrazoles充当用于二乙基锌（手性催化剂1）除了芳香醛和1-芳基-1-丙醇进行对映选择性地得到。这些反应在30摩尔％（2'S）-2-（2-苯基-2-羟乙基）-3-苯基-1-men-吡唑（（S）-16d），得到高达70％ee（S）的旋光1-芳基-1-丙醇。
• A practical method for the aziridination of α,β-unsaturated carbonyl compounds with a simple carbamate utilizing sodium hypochlorite pentahydrate
  作者：Takehiro Umeda、Satoshi Minakata

  DOI：10.1039/d1ra04297a

  日期：——

  N-chloro-N-sodio-carbamate by the reaction of simple tert-butyl carbamate with sodium hypochlorite pentahydrate (NaOCl·5H2O) would be a practical and green method for the aziridination of α,β-unsaturated carbonyl compounds. The process described herein is transition-metal free, all of the materials are commercially available, the byproducts (NaCl and H2O) are environmentally benign and the reaction is stereoselective

  简单的氨基甲酸叔丁酯与五水合次氯酸钠(NaOCl·5H 2 O)反应高效生成N-氯代-N-钠-氨基甲酸叔丁酯是一种实用且绿色的α,β氮丙啶化方法-不饱和羰基化合物。本文所述的方法不含过渡金属，所有材料均可商购，副产物（NaCl 和 H 2 O）对环境无害且反应具有立体选择性。所得氮丙啶是氨基酸的潜在前体。
• Asymmetric diels alder reaction using pyrazole derivatives as a chiral catalyst
  作者：Choji Kashima、Yohei Miwa、Saori Shibata、Hiroyuki Nakazono

  DOI：10.1002/jhet.5570400420

  日期：2003.7

  promising as good dienophiles, which were easily converted into the desired carboxylic derivatives. Bis(pyrazolyl)methanes, which were derived from chiral pyrazoles, showed the activity of chiral catalyst. Particularly 10 mol% of bis(isomenthopyrazol-1,1′-yl)methane (8a) catalyzed enantioselectively the Diels Alder reaction up to 40 % ee by the formation of complex with Mg(ClO4)2.

  N-酰基吡唑类（1）具有良好的二烯亲和性，有望轻松转化为所需的羧酸衍生物。衍生自手性吡唑的双（吡唑基）甲烷显示出手性催化剂的活性。通过与Mg（ClO 4）2形成络合物，特别是10 mol％的双（异薄荷基吡唑-1,1'-基）甲烷（8a）对映选择性地催化Diels Alder反应达到40％ee 。
• Asymmetric borane reduction of ketones promoted by menthopyrazole-zncl₂complex
  作者：Choji Kashima、Yoshihiro Tsukamoto、Yohei Miwa、Kohei Higashide

  DOI：10.1002/jhet.5570380308

  日期：2001.5

  The enantioselective reduction of ketones was accomplished by borane in the presence of pyrazole derivatives, particularly 2-methoxymethyl-3-phenyl-1-menthopyrazole (8). The catalysis of zinc chloride makes it possible to lower the reaction temperature below 0 °C, and to promote enantioselectivity.

  在吡唑衍生物，特别是2-甲氧基甲基-3-苯基-1-薄荷基吡唑（8）的存在下，通过硼烷完成对映体酮的对映选择性还原。氯化锌的催化使得可以将反应温度降低至低于0℃，并促进对映选择性。
• Asymmetric borane reduction of ketones catalyzed by<i>N</i>-hydroxyalkyl-<i>l</i>-menthopyrazoles
  作者：Choji Kashima、Yoshihiro Tsukamoto、Kohei Higashide、Hiroyuki Nakazono

  DOI：10.1002/jhet.5570370449

  日期：2000.7

  N-(hydroxyalkyl)pyrazoles and borane formed boric ester complex, in which the remaining borane was stabilized by the adjacent nitrogen of thr pyrazole ring. The borane complex derived from the chiral pyrazoles such as 3-phenyl-l-menthopyrazole reduced p-methylacetophenone (21) enantioselectively. When (2′S)-2-(2′-phenyl-2′-hydroxyethyl)-3-phenyl-l-menthopyrazole ((2′S)-10b) was used, 21 was reduced into (

  N-（羟烷基）吡唑与硼烷的等摩尔混合物形成硼酸酯络合物，其中剩余的硼烷被吡唑环的相邻氮原子稳定。衍生自手性吡唑的硼烷络合物，例如3-苯基-1-薄荷基吡唑，对映体选择性还原对甲基苯乙酮（21）。当使用（2 'S）-2-（2'-苯基-2'-羟乙基）-3-苯基-1-薄荷基吡唑（（2 'S）-10b）时，将21还原为（S）-p-。甲基苯基-1-乙醇（22）的化学和光学收率中等。由于制备的不便和较低的光学收率，使用N-（α-羟烷基）吡唑对硼烷的对映体选择性还原酮是没有希望的。