(1S,3R)-3-(1-isobutenyl)-2,2-dimethylcyclopropanecarboxylic acid | 84848-28-2

• 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: (1S,3R)-3-(1-isobutenyl)-2,2-dimethylcyclopropanecarboxylic acid
• 英文别名: cis-tert-butyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate；tert-butyl (1S,3R)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate
• CAS: 84848-28-2
• 化学式: C₁₄H₂₄O₂
• 分子量: 224.343
• InChiKey: YDNUIHHAHDMFJZ-GHMZBOCLSA-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

• 作为反应物：
  描述：

  (1S,3R)-3-(1-isobutenyl)-2,2-dimethylcyclopropanecarboxylic acid 在 potassium tert-butylate 、 硫酸 、 水 作用下， 以 苯 为溶剂， 生成 (+)-反式-菊酸
  参考文献：
  名称：

  Selected regiocontrolled transformations applied to the synthesis of (1S)-cis-chrysanthemic acid from (1S)-3,4-epoxy-2,2,5,5-tetramethylcyclohexanol

  摘要：

  (1S)-顺式-菊酸的制备包括几个步骤，通过控制相对和绝对立体化学，使用区域控制的环氧化物开环、二醇单氧化和环丙烷化。

  DOI：

  10.1039/b808695h
• 作为产物：
  描述：

  异丁烯 、 cis-Chrysanthemic acid 在 硫酸 作用下， 生成 (1S,3R)-3-(1-isobutenyl)-2,2-dimethylcyclopropanecarboxylic acid
  参考文献：
  名称：

  Selected regiocontrolled transformations applied to the synthesis of (1S)-cis-chrysanthemic acid from (1S)-3,4-epoxy-2,2,5,5-tetramethylcyclohexanol

  摘要：

  (1S)-顺式-菊酸的制备包括几个步骤，通过控制相对和绝对立体化学，使用区域控制的环氧化物开环、二醇单氧化和环丙烷化。

  DOI：

  10.1039/b808695h

文献信息

• Enantioselectivity and<i>cis</i>/<i>trans</i>-Selectivity in Dirhodium(II)-Catalyzed addition of diazoacetates to olefins
  作者：Paul Müller、Corine Baud、Doïna Ené、Sharokh Motallebi、Michael P. Doyle、Bridget D. Brandes、Alexey B. Dyatkin、Marjorie M. See

  DOI：10.1002/hlca.19950780217

  日期：1995.3.22

  comparable. Additions catalyzed by 1 are strongly sensitive to steric effects. Highly substituted olefins afford cyclopropanes in only poor yield. The preferential cis-selectivity observed in reactions catalyzed by 1 is attributed to dominant interactions between the ligand of the catalyst and the substituents of both olefin and diazoacetate, which overrule the steric interactions between olefin and diazoacetate

  用[Rh 2 （4 S）-phox} 4 ]（1 ; phox =四[[4 S）-四氢-4-苯基恶唑-2-酮]）研究了Rh 11催化的重氮乙酸类酯类化合物向烯烃的加成反应。，[Rh 2 （（2 S）-mepy} 4 ]（2 ; mepy =四[甲基（2 S）-四氢-5-氧杂吡咯-2-羧酸酯]）和[Rh 2（OAc）4 ]（3）。当用2和3催化时，优先提供反式-环丙烷羧酸酯，顺式-异构体是1的主要产品。通常，用1和2获得的对映选择性是可比较的。1催化的加成对位阻效应非常敏感。高度取代的烯烃仅以较差的收率提供环丙烷。在1催化的反应中观察到的优先顺式选择性归因于催化剂的配体与烯烃和重氮乙酸酯的取代基之间的显性相互作用，该相互作用抵消了烯烃和重氮乙酸酯在过渡态下的卡宾转移的空间相互作用。
• 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.
• Demonceau, A.; Noels, A. F.; Anciaux, A. J., Bulletin des Societes Chimiques Belges, 1984, vol. 93, # 11, p. 949 - 952
  作者：Demonceau, A.、Noels, A. F.、Anciaux, A. J.、Hubert, A. J.、Teyssie, P.

  DOI：——

  日期：——
• OPTICALLY ACTIVE BISOXAZOLINE COMPOUNDS, PROCESS FOR PRODUCTION OF THE SAME AND USE THEREOF
  申请人：Sumitomo Chemical Company, Limited

  公开号：EP1593674B1

  公开（公告）日：2011-07-20
• 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.