4-tert-butyl-4,5-dihydro-2-(2,3,3-trimethylbutan-2-yl)oxazole | 852524-85-7

• 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: 4-tert-butyl-4,5-dihydro-2-(2,3,3-trimethylbutan-2-yl)oxazole
• 英文别名: (4S)-4-tert-butyl-2-(2,3,3-trimethylbutan-2-yl)-4,5-dihydro-1,3-oxazole
• CAS: 852524-85-7
• 化学式: C₁₄H₂₇NO
• 分子量: 225.374
• InChiKey: JQVVZBFRGRJEEI-SNVBAGLBSA-N

物化性质

• 沸点：
  266.2±9.0 °C(Predicted)
• 密度：
  0.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  4-tert-butyl-4,5-dihydro-2-(2,3,3-trimethylbutan-2-yl)oxazole 在 palladium diacetate 、 碘苯二乙酸 、 碘 作用下， 以 二氯甲烷 为溶剂， 反应 30.0h， 以83%的产率得到(S)-4-tert-butyl-4,5-dihydro-2-(2-(iodomethyl)-3,3-dimethylbutan-2-yl)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：

  2,2,3,3-tetramethylbutyric acid chloride 在 三苯基膦 作用下， 生成 4-tert-butyl-4,5-dihydro-2-(2,3,3-trimethylbutan-2-yl)oxazole
  参考文献：
  名称：

  钯在温和条件下催化未活化CH键的不对称碘化。

  摘要：

  DOI：

  10.1002/anie.200462884

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。
• Understanding Reactivity and Stereoselectivity in Palladium-Catalyzed Diastereoselective sp³ C–H Bond Activation: Intermediate Characterization and Computational Studies
  作者：Ramesh Giri、Yu Lan、Peng Liu、K. N. Houk、Jin-Quan Yu

  DOI：10.1021/ja304643e

  日期：2012.8.29

  sp(3) C-H bond iodination and acetoxylation reactions as reported in previous publications has been studied and explained on the basis of experimental and computational investigations. The characterization of a trinuclear chiral C-H insertion intermediate by X-ray paved the way for further investigations into C-H insertion step through the lens of stereochemistry. Computational investigations on reactivities

  已经研究和解释了在恶唑啉导向、Pd(II) 催化的 sp(3) CH 键碘化和乙酰氧基化反应中观察到的高水平反应性和非对映选择性 (>99:1 dr) 的起源在实验和计算研究的基础上。X 射线对三核手性 CH 插入中间体的表征为通过立体化学镜头进一步研究 CH 插入步骤铺平了道路。对 t-Bu-和 i-Pr-取代的恶唑啉的 CH 活化的反应性和非对映选择性的计算研究与实验结果非常吻合。DFT 计算的理论预测表明 CH 活化发生在单体 Pd 中心，并且 CH 活化的最优选过渡态由于空间排斥而在反位包含两个空间庞大的 t-Bu 取代基，并且该过渡态导致主要非对映异构体，这与新表征的 CH 插入中间体的结构一致。关于过渡态的结构信息还表明 CH 键和 Pd-OAc 键之间的最小二面角对于 CH 键断裂至关重要。
• 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