(4S,7R)-4,7-甲桥-1H-吲唑 | 72345-25-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: (4S,7R)-4,7-甲桥-1H-吲唑
• 英文名称: (4S,7R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methano-2H-indazole
• 英文别名: (4S,7R)-4,7-Methano-1H-indazole；(1R,7S)-1,10,10-trimethyl-3,4-diazatricyclo[5.2.1.02,6]deca-2(6),4-diene
• CAS: 72345-25-6
• 化学式: C₁₁H₁₆N₂
• 分子量: 176.261
• InChiKey: IQTIQGVRWRCLOK-KCJUWKMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  (4S,7R)-4,7-甲桥-1H-吲唑 以 二氯甲烷 为溶剂， 反应 84.0h， 生成 (4S,7R)-2-(Diethylaminomethyl)-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methano-2H-indazole
  参考文献：
  名称：

  Chiral Heterocyclic Ligands. VIII. Syntheses and Complexes of New Chelating Ligands Derived From Camphor

  摘要：

  本文介绍了 23 种新型螯合配体的合成。这些配体大多来自手性吡唑（1），而吡唑（1）已与多种杂环连接，即吡啶、嘧啶、哒嗪、异噁唑、苯并咪唑、噻吩和呋喃。在某些情况下，还制备出了母体非手性类似物。对这些配体与某些过渡金属的配位化学进行了初步研究。此外，还测定了含异噁唑和噻吩配体的钯配合物的 X 射线晶体结构。

  DOI：

  10.1071/ch9951549
• 作为产物：
  描述：

  3-((二甲氨基)亚甲基)樟脑 在 盐酸肼 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以81%的产率得到(4S,7R)-4,7-甲桥-1H-吲唑
  参考文献：
  名称：

  Cyclocondensations of (+)-camphor derived enaminones with hydrazine derivatives

  摘要：

  Reactions of 3-[(E)-(dimethylamino)methylidene]-(+)-camphor and (1R,5S)-4-[(E)-(dimethylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one with hydrazine derivatives were studied. Treatment of 3-[(E)-(dimethylamino)methylidene]-(+)camphor with hydrazines afforded the corresponding fused pyrazoles. Similarly, fused pyrazoles were obtained upon reaction of (1R,5S)-4-[(E)-(dimethylamino)methylidene]-1,8,8-tritnethyl-2-oxabicyclo[3.2.1]octan-3-one with ortho-unsubstituted phenylhydrazines, while reactions with ortho-substituted phenylhydrazines and with hydrazine hydrochloride resulted in 'ring switching' type of transformation to furnish 2-aryl-4-[(1S, 3R)-3-hydroxy-2,2,3-trimethylcyclopentyl]-1,2-dihydro-3H-pyrazol-3-ones. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.02.048

文献信息

• Chiral bis(pyrazolyl)methane copper(I) complexes and their application in nitrene transfer reactions
  作者：Fabian Thomas、Dominik Steden、Alexander Eith、Alexander Hoffmann、Sonja Herres-Pawlis

  DOI：10.1515/znb-2021-0140

  日期：2021.11.25

  In this study, chiral bis(pyrazolyl)methane copper(I) acetonitrile complexes were applied to generate two novel terminal copper tosyl nitrene complexes with the nitrene generating agent SPhINTs in dichloromethane at low temperatures. The syntheses of the chiral bis(pyrazolyl)methane ligands are based on pulegone and camphor, members of the natural chiral pool. The chiral copper(I) acetonitrile complexes

  在这项研究中，手性双（吡唑基）甲烷铜（I）乙腈配合物被用于与氮烯发生剂生成两种新型末端甲苯磺酰基氮烯铜络合物。小号低温下二氯甲烷中的 PhINT。手性双（吡唑基）甲烷配体的合成基于天然手性库的成员胡薄荷酮和樟脑。手性铜 (I) 乙腈配合物在铜氮烯介导的不同苯乙烯衍生物的氮丙啶化反应和各种底物的 C-H 胺化反应中用作催化剂。该反应提供了良好的产率，但在温和条件下对映体过量较低。氮烯种类已通过紫外/可见光和 EPR 光谱以及 ESI 质谱的衰变产物进行了表征。
• Chiral C2 and C1 symmetric (cyclooctane-1,5-diyl)bis(2-pyrazolyl)borate complexes of potassium and thallium. Preparation, structures and solution behavior
  作者：Malcolm H. Chisholm、Suri S. Iyer、William E. Streib

  DOI：10.1039/a906582b

  日期：——

  The preparation, structures and solution behavior of (cyclooctane-1,5-diyl)bis[(4S,7R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methano-2H-indazol-2-yl]borato-κN1,κN1′}metal, where metal=K, 1, or Tl, 2, (cyclooctane-1,5-diyl)[(4S,7R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methano-2H-indazol-2-yl][(4S,7R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methano-2H-indazol-2-yl]borato-κN1,κN1′}potassium–tetrahydrofuran(1/3), 3·3THF, and (cyclooctane-1,5-diyl)bis[(4R,7R)-7-isopropyl-4-methyl-4,5,6,7-tetrahydro-2H-indazol-2-yl]borato-κN1,κN1′}potassium–tetrahydrofuran(1/4), 4·4THF, are reported.

  报告了(环辛烷-1,5-二基)双[(4S,7R)-7,8,8-三甲基-4,5,6,7-四氢-4,7-甲烷-2H-吲唑-2-基]硼酸-κN1,κN1'}金属的制备、结构和溶液行为，其中金属=K，1，或Tl，2，(环辛烷-1,5-二基)[(4S,7R)-7,8,8-三甲基-4,5,6,7-四氢-4,7-甲烷-2H-吲唑-2-基][(4S,7R)-7,8,8-三甲基-4,5,6,7-四氢-4,7-甲烷-2H-吲唑-2-基]硼酸-κN1,κN1'}钾–四氢呋喃(1/3)，3·3THF，以及(环辛烷-1,5-二基)双[(4R,7R)-7-异丙基-4-甲基-4,5,6,7-四氢-2H-吲唑-2-基]硼酸-κN1,κN1'}钾–四氢呋喃(1/4)，4·4THF。
• Chiral 1,8-naphthyridine based ligands: Syntheses and characterization of Di- and tetranuclear copper (I) and silver (I) complexes
  作者：Mithun Sarkar、Pragati Pandey、Jitendra K. Bera

  DOI：10.1016/j.ica.2018.11.014

  日期：2019.2

  scaffold to access chiral ligands L1, L2 and L3. Metalation of these chiral ligands with Cu(I) and Ag(I) precursors afforded di- and tetranuclear complexes [Cu4I4(L1)2] (1), [Cu4I4(L2)2] (2), [Cu2I2(L3)] (3), [Cu2I(L2)2](OTf) (4), [Ag2(L1)2](OTf)2 (5) and [Ag4(L2)4Br](OTf)3 (6), containing [M4Xn] (n = 1,4 and X = Br, I) or [M2Xn] (n = 0, 1, 2 and X = I) core. All complexes are structurally characterized

  摘要在1,8-萘啶骨架上引入了恶唑啉和樟脑-吡唑单元，以访问手性配体L1，L2和L3。这些手性配体与Cu（I）和Ag（I）前体的金属化提供了双核和四核配合物[Cu4I4（L1）2]（1），[Cu4I4（L2）2]（2），[Cu2I2（L3）] （3），[Cu2I（L2）2]（OTf）（4），[Ag2（L1）2]（OTf）2（5）和[Ag4（L2）4Br]（OTf）3（6），含有[ M4Xn]（n = 1,4和X = Br，I）或[M2Xn]（n = 0、1、2和X = I）磁芯。所有复合物均具有结构特征。萘啶衍生的配体揭示了桥螯合物配位基序，并保持两个金属中心非常接近。四核配合物是由卤化物桥接的双核配合物的二聚体。报道了铜络合物的电子吸收和发射光谱。检查了所有配合物的催化效用是否不对称转化，但它们显示出较差的活性，这可能是由于金属中心的溶解度有限和配位饱和所致。用[L3 / Cu盐]组合以
• Synthesis of Novel Chiral Diazole Derivative Ligands for the Enantioselective Addition of Diethylzinc to Benzaldehyde
  作者：Hiyoshizo Kotsuki、Masahiro Wakao、Hiroyuki Hayakawa、Tomoyasu Shimanouchi、Motoo Shiro

  DOI：10.1021/jo961388c

  日期：1996.1.1

  The high-pressure-promoted reaction of epoxides with pyrazoles and imidazoles provided access to a variety of chiral diazole derivative ligands such as 11-23. Furthermore, chiral pyrazoles 26 and 27, which have a primary alcohol side chain, were also prepared from (+)-camphopyrazole 4. Each of these chiral diazole ligands was used for the catalytic enantioselective addition of diethylzinc to benzaldehyde

  环氧化物与吡唑和咪唑的高压促进反应提供了接触各种手性二唑衍生物配体的途径，例如11-23。此外，还由（+）-樟脑吡唑4制备了具有伯醇侧链的手性吡唑26和27。这些手性二唑配体中的每一种都用于将二乙基锌催化对映选择性加成至苯甲醛。对于16和18，获得了最佳结果：在两种情况下均达到93％ee，并且观察到反向不对称诱导。在X射线晶体学数据的基础上，提供了一种有效的不对称感应机制。
• 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 。