tert-butyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropane-1-carboxylate | 851667-90-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: tert-butyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropane-1-carboxylate
• 英文别名: (1S,3S)-3-(1-isobutenyl)-2,2-dimethylcyclopropanecarboxylic acid；trans-Chrysanthemum-monocarbonsaeure-tert.-butylester；tert-butyl (1S,3S)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate
• CAS: 851667-90-8
• 化学式: C₁₄H₂₄O₂
• 分子量: 224.343
• InChiKey: YDNUIHHAHDMFJZ-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,5-二甲基-2,4-己二烯 、 重氮基乙酸叔丁酯 在 copper(I) trifluoromethanesulfonate benzene 、 C₂₈H₂₀Cl₄N₂ 作用下， 以 二氯甲烷 为溶剂， 反应 1.25h， 生成 (1R,3R)-3-(1-isobutenyl)-2,2-dimethylcyclopropanecarboxylic acid 、 tert-butyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropane-1-carboxylate
  参考文献：
  名称：

  Catalyst structure and the enantioselective cyclopropanation of alkenes by copper complexes of biaryldiimines: the importance of ligand acceleration

  摘要：

  The use of chiral non-racemic biaryl copper(I) complexes in the enantioselective cyclopropanation of a number of olefins with either ethyl or tert-butyl diazoacetate: is described. Lack of ligand acceleration and the presence of equilibrium amounts of catalytically active uncomplexed Cu(I) ions account for lowered enantioselectivity when using certain ligands. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00157-4

文献信息

• 铜催化烯烃的不对称环丙烷化方法及其应用
  申请人：中国科学院大连化学物理研究所

  公开号：CN112824372A

  公开（公告）日：2021-05-21

  本发明公开了一种铜催化烯烃的不对称环丙烷化方法及其应用。方法采用的铜催化剂是由金属铜前驱体与手性P,N,N‑配体在反应介质中原位生成的。本发明具有催化剂廉价、配体制备简单、高活性、高选择性、反应条件温和、操作简便等特点，且可实现连续操作，适用于大规模工业化生产中。本发明所述方法同样适用于杀虫剂拟除虫菊酯类农药的重要中间体—手性第一菊酸的不对称合成中，可达到80％收率，85％对映选择性，且可应用于工业化制备中。
• Highly efficient chiral copper Schiff-base catalyst for asymmetric cyclopropanation of 2,5-dimethyl-2,4-hexadiene
  作者：Makoto Itagaki、Koji Hagiya、Masashi Kamitamari、Katsuhisa Masumoto、Katsuhiro Suenobu、Yohsuke Yamamoto

  DOI：10.1016/j.tet.2004.06.073

  日期：2004.8

  A remarkable increase in catalytic activity is found for the asymmetric cyclopropanation of 2,5-dimethyl-2,4-hexadiene with diazoacetate by use of the chiral copper Schiff-base complexes, which are derived from substituted salicylaldehydes, chiral aminoalcohols, and copper acetate monohydrate. Furthermore, a combination of a chiral copper Schiff-base with a Lewis acid showed an increase in yield (up to 90%) and in enantioselectivity (up to 90% ee) for the asymmetric cyclopropanation of the diene with t-butyl diazoacetate at 20degreesC. (C) 2004 Elsevier Ltd. All rights reserved.
• Studies of Copper−Bisoxazoline-Catalyzed Asymmetric Cyclopropanation of 2,5-Dimethyl-2,4-hexadiene
  作者：Makoto Itagaki、Katsuhisa Masumoto、Katsuhiro Suenobu、Yohsuke Yamamoto

  DOI：10.1021/op050203d

  日期：2006.3.1

  In the [bis(4R)-(1-naphthyl)-5,5-diniethyloxazoline}/copper]catalyzed asymmetric cyclopropanation of 2,5-dimethyl-2,4-hexadiene with tert-butyl diazoacetate, the effects of a counterion of the copper complex were studied. The[CuCl/bisoxazoline/ Ph3CPF6] catalyst was found to enhance both the catalytic efficiency and the stereoselectivity (the catalyst 0.2 mol %, yield 92%, trans/cis = 88/12, 96% ee for the trans product), compared to our previously reported CuOTf/bisoxazoline catalyst. The density functional calculations were performed to elucidate the effects of the counterion as well as the effects of the gem-dimethyl groups at the 5-position on the bisoxazoline ligand.