2,2'-(1-allylbut-3-enylidene)bis[(4S)-4-tert-butyl-4,5-dihydro-2-oxazole]

• 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: 2,2'-(1-allylbut-3-enylidene)bis[(4S)-4-tert-butyl-4,5-dihydro-2-oxazole]
• 英文别名: 2,2'-(1-allylbut-3-enylidene)bis[(4S)-4-t-butyl-4,5-dihydro-2-oxazole]；t-Bu2-DABox；(4S)-4-tert-butyl-2-[4-[(4S)-4-tert-butyl-4,5-dihydro-1,3-oxazol-2-yl]hepta-1,6-dien-4-yl]-4,5-dihydro-1,3-oxazole
• 化学式: C₂₁H₃₄N₂O₂
• 分子量: 346.513
• InChiKey: AVESOMXECLXFMI-HZPDHXFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2,2′-亚甲基双[(4,s)-4-叔丁基-2-噁唑啉] 、 3-溴丙烯 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 25.0h， 以260 mg的产率得到2,2'-(1-allylbut-3-enylidene)bis[(4S)-4-tert-butyl-4,5-dihydro-2-oxazole]
  参考文献：
  名称：

  嵌入聚硅氧烷凝胶中的手性双（恶唑啉）配体：在可重复使用的铜催化剂上用于不对称环丙烷化的应用

  摘要：

  在“框” ED：一种新颖的聚硅氧烷凝胶包封的Cu II /双（恶唑啉）（铜II /箱）物种合成并用作与烯烃的不对称环丙烷可回收催化剂大号-薄荷基重氮基。

  DOI：

  10.1002/asia.201000527
• 作为试剂：
  描述：

  苯乙烯 、 重氮乙酸乙酯 在 copper(II) bis(trifluoromethanesulfonate) 、 2,2'-(1-allylbut-3-enylidene)bis[(4S)-4-tert-butyl-4,5-dihydro-2-oxazole] 作用下， 以 癸烷 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 ethyl (S,S)-2-phenylcyclopropane-1-carboxylate 、 ethyl (1S,2R)-2-phenylcyclopropylcarboxylate 、 (1R,2S)-ethyl 2-phenylcyclopropane-1-carboxylate 、 2-苯基环丙烷羧酸乙酯
  参考文献：
  名称：

  Bis(oxazoline)copper Complexes Covalently Bonded to Insoluble Support as Catalysts in Cyclopropanation Reactions

  摘要：

  Chiral bis(oxazolines) are readily dialkylated in the methylene bridge, opening the way to immobilization at that position, keeping the C-2 symmetry of the chiral ligand. Bis(oxazolines) functionalized with two allyl or vinylbenzyl groups are easily grafted onto mercaptopropylsilica. Another approach to immobilization is the polymerization of the ligands bearing vinylbenzyl groups to yield insoluble polymers. The Cu(OTf)(2) complexes of the immobilized ligands promote the enantioselective cyclopropanation reaction between styrene and ethyl diazoacetate. The results depend on the nature of the support and the method of immobilization. With regard to the type of solid, the best results, which are similar to or even better than those obtained with the corresponding dibenzylated homogeneous catalysts, are obtained with homopolymers. With regard to the bis(oxazoline), that bearing indan groups leads to good results both onto silica and polymers, whereas with the ligand bearing tert-butyl groups good enantioselectivities are only obtained with homopolymeric catalysts. Some of the heterogeneous catalysts can be easily recovered and reused, as much as five times, with the same yield and stereoselectivities.

  DOI：

  10.1021/jo0159338

文献信息

• Bis(oxazoline)copper Complexes Covalently Bonded to Insoluble Support as Catalysts in Cyclopropanation Reactions
  作者：M. Isabel Burguete、José M. Fraile、José I. García、Eduardo García-Verdugo、Clara I. Herrerías、Santiago V. Luis、José A. Mayoral

  DOI：10.1021/jo0159338

  日期：2001.12.1

  Chiral bis(oxazolines) are readily dialkylated in the methylene bridge, opening the way to immobilization at that position, keeping the C-2 symmetry of the chiral ligand. Bis(oxazolines) functionalized with two allyl or vinylbenzyl groups are easily grafted onto mercaptopropylsilica. Another approach to immobilization is the polymerization of the ligands bearing vinylbenzyl groups to yield insoluble polymers. The Cu(OTf)(2) complexes of the immobilized ligands promote the enantioselective cyclopropanation reaction between styrene and ethyl diazoacetate. The results depend on the nature of the support and the method of immobilization. With regard to the type of solid, the best results, which are similar to or even better than those obtained with the corresponding dibenzylated homogeneous catalysts, are obtained with homopolymers. With regard to the bis(oxazoline), that bearing indan groups leads to good results both onto silica and polymers, whereas with the ligand bearing tert-butyl groups good enantioselectivities are only obtained with homopolymeric catalysts. Some of the heterogeneous catalysts can be easily recovered and reused, as much as five times, with the same yield and stereoselectivities.
• A Chiral Bis(oxazoline) Ligand Embedded into Polysiloxane Gel: Application to a Reusable Copper Catalyst for Asymmetric Cyclopropanation
  作者：Yukihiro Motoyama、Takashi Nishikata、Hideo Nagashima

  DOI：10.1002/asia.201000527

  日期：2011.1.3

  “Box”ed in: A novel polysiloxane gel encapsulated CuII/bis(oxazoline) (CuII/Box) species was synthesized and used as a recyclable catalyst in the asymmetric cyclopropanation of alkenes with L‐menthyl diazoacetate.

  在“框” ED：一种新颖的聚硅氧烷凝胶包封的Cu II /双（恶唑啉）（铜II /箱）物种合成并用作与烯烃的不对称环丙烷可回收催化剂大号-薄荷基重氮基。