(4R,4’R)-2,2’-亚甲基双[4,5-二氢-4-(1-甲基乙基)噁唑] | 164976-63-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 中文名称: (4R,4’R)-2,2’-亚甲基双[4,5-二氢-4-(1-甲基乙基)噁唑]
• 英文名称: 2,2'-methylenebis[(4S)-4-isopropyl-2-oxazoline]
• 英文别名: 2,2'-methylenebis[(4R)-4-isopropyl-2-oxazoline]；2,2'-methylenebis((4S)-4-iso-propyl-2-oxazoline)；(4R,4'R)-2,2'-methylenebis[4,5-dihydro-4-(1-methylethyl)oxazole]；(4R)-4-propan-2-yl-2-[[(4R)-4-propan-2-yl-4,5-dihydro-1,3-oxazol-2-yl]methyl]-4,5-dihydro-1,3-oxazole
• CAS: 164976-63-0
• 化学式: C₁₃H₂₂N₂O₂
• 分子量: 238.33
• InChiKey: KEHOIBBPRFRZFW-QWRGUYRKSA-N

物化性质

• 沸点：
  308.1±25.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险性防范说明：
  P261,P280,P301+P312,P302+P352,P305+P351+P338
• 危险性描述：
  H302,H315,H320,H335

反应信息

• 作为反应物：
  描述：

  tetrakis(diethylamido)titanium(IV) 、 (4R,4’R)-2,2’-亚甲基双[4,5-二氢-4-(1-甲基乙基)噁唑] 以 甲苯 为溶剂， 以87%的产率得到
  参考文献：
  名称：

  Singh, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 1997, vol. 27, # 1, p. 155 - 166

  摘要：

  DOI：
• 作为产物：
  描述：

  L-缬氨酸 、 diethyl malonoimidate dihydrochloride 以 二氯甲烷 为溶剂， 生成 (4R,4’R)-2,2’-亚甲基双[4,5-二氢-4-(1-甲基乙基)噁唑]
  参考文献：
  名称：

  Spectroscopic studies on complexes of magnesium (II) with C2-chiral bis-oxazolines

  摘要：

  The configurations of chloro, ethyl and bis-complexes of magnesium with C-2-chiral bis-oxazolines such as 2,2'-methylenebis[(4S)-4-iso-propyl-2-oxazoline] (MBIO), 2,2'-methylenebis[(4S)-4-tert-butyl-2-oxazoline] (MBTO) and 2,2'-methylenebis[(4S)-4-phenyl-2-oxazoline] (MBPO) have been investigated on the basis of spectroscopic studies. The IR and NMR (H-1, C-13) data suggested that the bis-oxazoline ligands coordinated magnesium (II) through both the nitrogen atoms. The molecular weight determination in nitrobenzene indicated the dimeric nature of chloro and ethylmagnesium complexes whereas bis-magnesium complexes were found to be monomeric. (C) 1997 Elsevier Science B.V.

  DOI：

  10.1016/s1386-1425(97)00068-1
• 作为试剂：
  描述：

  6,7-二甲氧基-3,4-二氢异喹啉 、 bromozinc(1+),prop-1-ene 在 2,2'-联吡啶 、 正丁基锂 、 (4R,4’R)-2,2’-亚甲基双[4,5-二氢-4-(1-甲基乙基)噁唑] 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 (S)-1-allyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 、 (R)-1-allyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  A Concise Total Synthesis of (+)-Tetrabenazine and (+)-α-Dihydrotetrabenazine

  摘要：

  AbstractHighly concise asymmetric total syntheses of (+)‐tetrabenazine (1), a drug for the treatment of chorea associated with Huntington’s disease, and of (+)‐α‐dihydrotetrabenazine (2), an active metabolite of 1, have been accomplished. Our synthetic route features a trans‐selective enol etherification, followed by an unprecedented cation‐dependent aza‐Claisen rearrangement to establish the carbon framework and two stereogenic centers of tetrabenazine. The syntheses consist of seven steps (34 % overall yield) for (+)‐2 and eight steps (22 % overall yield) for (+)‐1.

  DOI：

  10.1002/chem.200902591

文献信息

• NOVEL PROCESSES FOR THE PREPARATION OF PHENYLCYCLOPROPYLAMINE DERIVATIVES AND USE THEREOF FOR PREPARING TICAGRELOR
  申请人：Khile Anil Shahaji

  公开号：US20130165696A1

  公开（公告）日：2013-06-27

  Provided herein are novel processes for the preparation of phenylcyclopropylamine derivatives, which are useful intermediates in the preparation of triazolo[4,5-d]pyrimidine compounds. Provided particularly herein are novel, commercially viable and industrially advantageous processes for the preparation of a substantially pure ticagrelor intermediate, trans-(1R,2S)-2-(3,4-difluorophenyl)-cyclopropylamine. Provided further herein are novel acid addition salts of trans-(1R,2S)-2-(3,4-difluorophenyl)-cyclopropylamine, and process for their preparation. The intermediate and its acid addition salts are useful for preparing ticagrelor, or a pharmaceutically acceptable salt thereof, in high yield and purity.

  本文提供了一种制备苯基环丙胺衍生物的新型工艺，这些衍生物在三唑并[4,5-d]嘧啶化合物的制备中是有用的中间体。特别提供了一种新颖、商业可行且在工业上具有优势的工艺，用于制备一种基本纯的替卡格雷中间体，即trans-(1R,2S)-2-(3,4-二氟苯基)-环丙胺。此外，本文还提供了trans-(1R,2S)-2-(3,4-二氟苯基)-环丙胺的新型酸加盐，以及其制备工艺。该中间体及其酸加盐对于高产率和纯度制备替卡格雷或其药用可接受盐是有用的。
• Asymmetric copper complex and cyclopropanation reaction using the same
  申请人：——

  公开号：US20020177718A1

  公开（公告）日：2002-11-28

  There are disclosed asymmetric copper complex comprising, as components, (a) an optically active bisoxazoline compound of formula (1): 1 wherein R 1 and R 2 are different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl or aralkyl group which may be substituted, R 3 and R 4 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl or aralkyl group which may be substituted, or R 3 and R 4 may be bonded to each other to form a C 3-5 cyclic alkylene group, R 5 represents a hydrogen atom or a C 1-6 alkyl group, or the two R 5 groups may be bonded to each other to represent a C 3-5 cyclic alkylene group, (b) a monovalent or divalent copper compound, and (c) a strong acid or a Lewis acid or a mixture thereof, and a process for producing an optically active cyclopropanecarboxylate using the same.

  揭示了包括以下组分的不对称铜络合物：（a）公式（1）的手性双噁唑啉化合物：其中R1和R2不同，每个代表氢原子、烷基、环烷基、苯基或芳基烷基，可能被取代，R3和R4每个代表氢原子、烷基、环烷基、苯基或芳基烷基，可能被取代，或者R3和R4可以相互连接形成C3-5环烷基，R5代表氢原子或C1-6烷基，或者两个R5基团可以相互连接形成C3-5环烷基；（b）一价或二价铜化合物；和（c）强酸或Lewis酸或二者混合物，以及使用它们制备手性环丙烷羧酸酯的方法。
• Method for producing optically active chrysanthemic acid
  申请人：SUMITOMO CHEMICAL COMPANY, LIMITED

  公开号：US20020123645A1

  公开（公告）日：2002-09-05

  Disclosed is a method for producing an optically active chrysanthemic acid, which method is characterized by optical resolution of a chrysanthemic acid having a trans isomer ratio of not less than 70% and an optical purity of 2% e.e. to less than 10% e.e. with an optically active organic.

  公开了一种生产光学活性菊酯酸的方法，该方法的特征是利用光学活性有机物对具有不低于70%的顺式异构体比率和2% e.e.至少10% e.e.的光学纯度的菊酯酸进行光学分辨。
• 2'-HYDROXYL-PROTECTED RIBONUCLEOSIDE DERIVATIVE AND MANUFACTURING METHOD OF SAME
  申请人：Kaneka Corporation

  公开号：EP2258709A1

  公开（公告）日：2010-12-08

  The present invention relates to a method for producing a 2'-hydroxy-protected nucleoside derivative by reacting a ribonucleoside with an acylating reagent in the presence of a metal complex consisting of a copper compound and an optically active ligand. By the method according to the present invention, a 2'-hydroxy-protected ribonucleoside derivative, which is an important intermediate for producing an oligonucleoside, can be easily produced with good regioselectivity from a nucleoside derivative of which 2',3'-hydroxy groups are not protected.

  本发明涉及一种通过在铜化合物和光学活性配体组成的金属配合物存在下，将核糖核苷与酰化试剂反应以制备2'-羟基保护核苷衍生物的方法。根据本发明的方法，可以从未保护2'、3'-羟基的核苷衍生物中轻松、有良好的区域选择性地制备重要的2'-羟基保护核糖核苷衍生物，该衍生物是合成寡核苷酸的重要中间体。
• 2'-HYDROXY-PROTECTED RIBONUCLEOSIDE DERIVATIVE AND PRODUCTION METHOD THEREOF
  申请人：Maeda Hirofumi

  公开号：US20110009609A1

  公开（公告）日：2011-01-13

  The present invention relates to a method for producing a 2′-hydroxy-protected nucleoside derivative by reacting a ribonucleoside with an acylating reagent in the presence of a metal complex consisting of a copper compound and an optically active ligand. By the method according to the present invention, a 2′-hydroxy-protected ribonucleoside derivative, which is an important intermediate for producing an oligonucleoside, can be easily produced with good regioselectivity from a nucleoside derivative of which 2′,3′-hydroxy groups are not protected.

  本发明涉及一种通过在存在铜化合物和光学活性配体组成的金属配合物的条件下，将核苷与酰化试剂反应，制备2'-羟基保护核苷衍生物的方法。根据本发明的方法，可以从未保护2'、3'-羟基的核苷衍生物中，以良好的区域选择性轻松地制备出2'-羟基保护的核苷衍生物，该衍生物是合成寡核苷酸的重要中间体。