(R)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole | 117408-98-7

• 物质功能分类: 化学试剂 - 有机试剂 - 膦配体
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (R)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole
• 英文别名: (R)-t-BuPyOx；2-[(4R)-4-tert-Butyl-4,5-dihydro-2-oxazolyl]pyridine；(4R)-4-tert-butyl-2-pyridin-2-yl-4,5-dihydro-1,3-oxazole
• CAS: 117408-98-7
• 化学式: C₁₂H₁₆N₂O
• 分子量: 204.272
• InChiKey: JDOAIDZRVWJBEG-JTQLQIEISA-N

物化性质

• 熔点：
  70.0 to 74.0 °C
• 沸点：
  125-135 °C(Press: 0.1 Torr)
• 密度：
  1.08±0.1 g/cm3(Predicted)
• 溶解度：
  略溶。在二氯甲烷中

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26
• 危险类别码：
  R36/38
• WGK Germany：
  3
• 危险性防范说明：
  P305+P351+P338
• 危险性描述：
  H315,H319

制备方法与用途

(S)-4-叔丁基-2-(2-氮苯基)恶唑啉可用作手性催化剂和噁唑啉配体。

反应信息

• 作为反应物：
  描述：

  gold(III) bromide 、 (R)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole 、 双三氟甲烷磺酰亚胺银盐 以 乙腈 为溶剂， 反应 0.25h， 以97%的产率得到[Au(Br₂)((R)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole)]⁺NTf₂^-
  参考文献：
  名称：

  Mechanism of Au(III)-Mediated Alkoxycyclization of a 1,6-Enyne

  摘要：

  Gold-mediated homogeneous catalysis is a powerful tool for construction of valuable molecules and has lately received growing attention. Whereas Au(I)-catalyzed processes have become well established, those mediated by Au(III) have so far barely been explored, and their mechanistic understanding remains basic. Herein, we disclose the combined NMR spectroscopic, single-crystal X-ray crystallographic, and computational (DFT) investigation of the Au(III)-mediated alkoxycyclization of a 1,6-enyne in the presence of a bidentate pyridine-oxazoline ligand. The roles of the counterion, the solvent, and the type of Au(III) complex have been assessed. Au(III) is demonstrated to be the active catalyst in alkoxycyclization. Alkyne coordination to Au(III) involves decoordination of the pyridine nitrogen and is the rate-limiting step.

  DOI：

  10.1021/jacs.9b09108
• 作为试剂：
  描述：

  呋喃甲酰氯 、 potassium α-benzyloxymethyltrifluoroborate 在 氯化镍二甲氧基乙烷 、 (R)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole 、 bis[3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridyl]phenyl]iridium(1+); 2-(2-pyridyl)pyridine; hexafluorophosphate 、 caesium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以36%的产率得到2-(benzyloxy)-1-(furan-2-yl)ethanone
  参考文献：
  名称：

  酰氯与烷氧基甲基三氟硼酸钾的可见光光氧化还原交叉偶联：α-烷氧基酮的合成

  摘要：

  已经开发了用于合成α-烷氧基酮的可见光，单电子转移（SET），光氧化还原交叉偶联。在这种方法中，成功地将各种脂肪族和芳香族酰氯与结构多样的烷氧基甲基三氟硼酸钾偶联，从而以高收率生产出相应的α-烷氧基酮。在这种操作简单且温和的交叉偶联方案中，所需的酮可通过一种对烷基硼化学和光氧化还原/ Ni催化均具有独特作用的键合连接，从稳定的起始原料中一步获得所需的酮。

  DOI：

  10.1021/acs.orglett.5b03705

文献信息

• Arene ruthenium complexes with pyridyloxazolines: synthesis and applications as asymmetric catalysts for Diels–Alder reactions †
  作者：Adam J. Davenport、David L. Davies、John Fawcett、Shaun A. Garratt、David R. Russell

  DOI：10.1039/b006530g

  日期：——

  Reaction of the dimers [RuCl2(arene)]2 with pyridyloxazolines (pymox) gave complexes [RuCl(pymox)(arene)][SbF6] 1–12 which have been fully characterised. Using chiral ligands diastereomers are formed, the diastereoselectivity depending on the substituents on the arene and on the oxazoline. The complexes [RuCl(Me2-pymox)(mes)][SbF6] 1, [RuCl(Ph-pymox)(mes)][SbF6] 3, [RuCl(iPr-pymox)(mes)][SbF6] 5 and [RuCl(indanyl-pymox)(mes)][SbF6] 12 (mes = mesitylene) have been characterised by X-ray crystallography. Treatment of these cations with AgSbF6 generates dications which in some cases can be isolated as aqua species [Ru(OH2)(pymox)(arene)]2+; these dications are enantioselective catalysts for Diels–Alder reactions of acroleins and dienes; a mechanism is proposed which accounts for the observed enantioselectivity.

  二聚体[RuCl2(arene)]2 与吡啶恶唑（hypmox）反应生成了[RuCl(hypmox)(arene)][SbF6] 1â12 复合物，对这些复合物进行了全面的表征。使用手性配体可形成非对映异构体，非对映选择性取决于炔和噁唑啉上的取代基。复合物 [RuCl(Me2-pymox)(mes)][SbF6]1、[RuCl(Ph-pymox)(mes)][SbF6]3、[RuCl(iPr-pymox)(mes)][SbF6]5 和 [RuCl(茚基-pymox)(mes)][SbF6]12（mes=mesitylene）已通过 X 射线晶体学进行了表征。用 AgSbF6 处理这些阳离子会产生二阳离子，在某些情况下，这些二阳离子可分离为水合物 [Ru(OH2)(pymox)(arene)]2+；这些二阳离子是丙烯醛和二烯的 DielsâAlder 反应的对映体选择性催化剂；提出了一种机制来解释所观察到的对映体选择性。
• Mechanism of Au(III)-Mediated Alkoxycyclization of a 1,6-Enyne
  作者：Ann Christin Reiersølmoen、Dániel Csókás、Imre Pápai、Anne Fiksdahl、Máté Erdélyi

  DOI：10.1021/jacs.9b09108

  日期：2019.11.13

  Gold-mediated homogeneous catalysis is a powerful tool for construction of valuable molecules and has lately received growing attention. Whereas Au(I)-catalyzed processes have become well established, those mediated by Au(III) have so far barely been explored, and their mechanistic understanding remains basic. Herein, we disclose the combined NMR spectroscopic, single-crystal X-ray crystallographic, and computational (DFT) investigation of the Au(III)-mediated alkoxycyclization of a 1,6-enyne in the presence of a bidentate pyridine-oxazoline ligand. The roles of the counterion, the solvent, and the type of Au(III) complex have been assessed. Au(III) is demonstrated to be the active catalyst in alkoxycyclization. Alkyne coordination to Au(III) involves decoordination of the pyridine nitrogen and is the rate-limiting step.