(S)-4-tert-butyl-2-(1-chloro-2-methylpropan-2-yl)-4,5-dihydrooxazole | 874135-69-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: (S)-4-tert-butyl-2-(1-chloro-2-methylpropan-2-yl)-4,5-dihydrooxazole
• 英文别名: (4S)-4-tert-butyl-2-(1-chloro-2-methylpropan-2-yl)-4,5-dihydro-1,3-oxazole
• CAS: 874135-69-0
• 化学式: C₁₁H₂₀ClNO
• 分子量: 217.739
• InChiKey: RJHBSWHTZMKNJY-MRVPVSSYSA-N

物化性质

• 沸点：
  256.9±23.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-4-tert-butyl-2-(1-chloro-2-methylpropan-2-yl)-4,5-dihydrooxazole 在 palladium diacetate 、 碘苯二乙酸 、 碘 作用下， 以 二氯甲烷 为溶剂， 反应 36.0h， 以60%的产率得到(S)-4-tert-Butyl-2-(1-chloromethyl-2-iodo-1-methyl-ethyl)-4,5-dihydro-oxazole
  参考文献：
  名称：

  Catalytic and stereoselective iodination of prochiral C–H bonds

  摘要：

  Oxazo lines were employed,as cyclic chiral directing groups for stereoselective C-H activation. Oxazoline-directed cleavage of the P-C-H bonds followed by reaction with I, gave a wide range of iodinated products. A large range of functional groups are tolerated. PdI2 was isolated in the reaction and found to be converted to Pd(OAc)(2) upon treatment with a combination Of I-2 and PhI(OAC)(2) in situ to achieve catalytic turnover. Diastereoselective iodination of prochiral C-H bonds were also investigated. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.08.049
• 作为产物：
  描述：

  氯代特戊酰氯 在 伯吉斯试剂 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 (S)-4-tert-butyl-2-(1-chloro-2-methylpropan-2-yl)-4,5-dihydrooxazole
  参考文献：
  名称：

  NeoPHOX-用于不对称催化的结构可调的配体系统。

  摘要：

  已开发出衍生自丝氨酸或苏氨酸的新NeoPHOX配体的合成。中心中间体是在紧靠恶唑啉N原子的立体异构中心带有甲氧基羰基的NeoPHOX衍生物。甲基氯化镁的加入产生了叔醇，其可以被酰化或甲硅烷基化以产生具有不同空间需求的NeoPHOX配体。在铱催化的不对称氢化和钯催化的烯丙基取代中测试了新的NeoPHOX配体。在这两个反应中，都实现了高对映选择性，这与使用目前为止从昂贵的叔亮氨酸衍生的最新最好的NeoPHOX配体所获得的对映选择性相当。

  DOI：

  10.3762/bjoc.12.114

文献信息

• [EN] CATALYTICS ASYMMETRIC ACTIVATION OF UNACTIVATED C-H BONDS, AND COMPOUNDS RELATED THERETO<br/>[FR] ACTIVATION CATALYTIQUE ASYMETRIQUE DE LIAISONS C-H INACTIVEES ET COMPOSES ASSOCIES
  申请人：UNIV BRANDEIS

  公开号：WO2006026053A1

  公开（公告）日：2006-03-09

  One aspect of the present invention is directed in part to catalytic and stereoselective functionalization of unactivated C-H bonds of simple organic substrates. The compounds and methods provided herein allow one to control the stereochemistry in a C-H activation step, activate substrates containing α-hydrogens next to the directing group, and remove a directing group under mild conditions. One aspect of the present invention relates to a transition-metal-catalyzed method for selective and asymmetric oxidation of carbons located in a β- or Ϝ-position relative to an auxiliary. Another aspect of the invention relates to the enantiomerically-enriched substrates and the enantiomerically-enriched products formed via said method. In certain embodiments, oxazoline and oxazinone directing groups are used. In addition, the Boc protecting group has been identified as a directing group which does not necessitate removal.

  本发明的一个方面部分涉及简单有机底物中未活化C-H键的催化和对映选择性官能团化。本发明提供的化合物和方法允许在C-H活化步骤中控制立体化学，活化含有邻近导向基团的α-氢的底物，并在温和条件下移除导向基团。本发明的另一方面涉及一种过渡金属催化的方法，用于选择性和非对称氧化位于辅助基团β-或Ϝ-位置上的碳。发明的另一个方面涉及通过所述方法形成的对映体富集的底物和对映体富集的产品。在某些实施例中，使用了恶唑啉和恶嗪酮导向基团。此外，Boc保护基团被识别为不需要移除的导向基团。
• NeoPHOX—an easily accessible P,N-ligand for iridium-catalyzed asymmetric hydrogenation: preparation, scope and application in the synthesis of demethyl methoxycalamenene
  作者：Marcus G. Schrems、Andreas Pfaltz

  DOI：10.1039/b912680e

  日期：——

  Using a new class of chiral iridium hydrogenation catalysts, the antitumor natural product demethyl calamenene was synthesized in four steps in >20% overall yield and high enantiomeric purity.

  采用新型手性铱氢化催化剂，抗肿瘤天然产物去甲基石竹烯经四步合成，总产率超过20%，且具有高度的手性纯度。
• A Unified Approach for the Stereoselective Total Synthesis of Pyridone Alkaloids and Their Neuritogenic Activity
  作者：Henning Jacob Jessen、Andreas Schumacher、Travis Shaw、Andreas Pfaltz、Karl Gademann

  DOI：10.1002/anie.201007671

  日期：2011.4.26

  neurite outgrowth might constitute a valuable approach for the non‐invasive medical treatment of neurodegenerative diseases. With the aid of a bifunctional building block, the total syntheses of a group of pyridone polyenes originally produced by entomopathogenic fungi was achieved (see picture). All of these natural products displayed neuritogenic activity in the PC‐12 cell line.

  随机性：诱导神经突生长的化合物的开发可能是神经退行性疾病的非侵入性医学治疗的一种有价值的方法。借助双功能构件，可以实现原本由病原性真菌产生的一组吡啶酮多烯的全部合成（见图）。所有这些天然产物在PC-12细胞系中均显示出神经生成活性。
• Chiral ligands
  申请人：Solvias AG

  公开号：EP2202236A1

  公开（公告）日：2010-06-30

  Chiral compounds of the formula (1), which are optically pure or highly optically enriched in which R0 is C1-C12-alkyl which is unsubstituted or substituted by 1 to 2 C1-C4-alkoxy; cyclopentyl or cyclohexyl, which is unsubstituted or substituted by 1 to 3 C1-C4-alkyl or C1-C4-alkoxy; or benzyl, phenyl or naphtyl which is unsubstituted or substituted by 1 to 3 C1-C4-alkyl, C1-C4-alkoxy, C1-C4-fluoroalkyl or C1-C4-fluoroalkoxy, F or Cl, each of R1 and R'1 independently is hydrogen or has the meaning of R0 whereby R1, R'1 and R0 can be same or different, R2 and R3 are independently a C-bonded hydrocarbon radical or a heterohydrocarbon radical, and each of both R4 is C1-C6-alkyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, methylbenzyl or benzyl, or both R4 together form an aliphatic C4-C6 carbocycle. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reaction, particularly hydrogenations.

  化学式（1）的手性化合物，其光学纯度高或光学富集，其中R0是未取代或取代1至2个C1-C4-烷氧基的C1-C12-烷基；环戊基或环己基，未取代或取代1至3个C1-C4-烷基或C1-C4-烷氧基；或苄基，苯基或萘基，未取代或取代1至3个C1-C4-烷基，C1-C4-烷氧基，C1-C4-氟烷基或C1-C4-氟烷氧基，F或Cl，R1和R'1中的每一个独立地是氢或具有R0的含义，其中R1，R'1和R0可以相同也可以不同，R2和R3独立地是C键合的碳氢基团或杂原子碳氢基团，R4中的每一个都是C1-C6-烷基，环戊基，环己基，苯基，甲基苯基，甲基苄基或苄基，或者两个R4一起形成一个脂肪族C4-C6碳环。这些配体的金属络合物是对不对称加成反应，尤其是氢化反应的均相催化剂。
• Pd-Catalyzed Stereoselective Oxidation of Methyl Groups by Inexpensive Oxidants under Mild Conditions: A Dual Role for Carboxylic Anhydrides in Catalytic CH Bond Oxidation
  作者：Ramesh Giri、Jue Liang、Jian-Guang Lei、Jiao-Jie Li、Dong-Hui Wang、Xiao Chen、Isaac Clement Naggar、Chengyun Guo、Bruce M. Foxman、Jin-Quan Yu

  DOI：10.1002/anie.200502767

  日期：2005.11.18