3-ethylcyclohex-2-enyl picolinate | 1428377-68-7

• 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: 3-ethylcyclohex-2-enyl picolinate
• 英文别名: (3-Ethylcyclohex-2-en-1-yl) pyridine-2-carboxylate；(3-ethylcyclohex-2-en-1-yl) pyridine-2-carboxylate
• CAS: 1428377-68-7
• 化学式: C₁₄H₁₇NO₂
• 分子量: 231.294
• InChiKey: OSQYAWQAJJMKGU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  39.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  溴丁基-镁 、 3-ethylcyclohex-2-enyl picolinate 在 copper(I) bromide dimethylsulfide complex 、 zinc(II) iodide 作用下， 以 四氢呋喃 为溶剂， 以79%的产率得到3-butyl-3-ethylcyclohexene
  参考文献：
  名称：

  Construction of quaternary carbon centers by using substitution of γ,γ-disubstituted secondary allylic picolinates with alkylcopper reagents

  摘要：

  ZnI2 was found to promote regio- and stereoselective substitution of gamma,gamma-disubstituted secondary allylic picolinates with alkylcopper reagents derived from alkyl-MgBr and CuBr center dot Me2S in a 2:1 ratio to furnish quaternary carbon centers in good yields. Alkyl groups delivered efficiently were the primary, secondary, and benzyl classes such as Me, Et, Bu, C16H33, Ph(CH2)(2), Ph(CH2)(3), c-C6H11, and Bn. As an application, allylic picolinates with the (E)- or (Z)-olefin afforded quaternary carbon centers that are the enantiomers of each other. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.06.046
• 作为产物：
  描述：

  2-吡啶甲酸 、 3-乙基环己-2-烯-1-醇 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 以83%的产率得到3-ethylcyclohex-2-enyl picolinate
  参考文献：
  名称：

  Allylic Substitution for Construction of a Chiral Quaternary Carbon Possessing an Aryl Group

  摘要：

  Phenylcopper reagents derived from 2:1 PhMgBr/Cu(acac)(2) and 3:1:1 PhMgBr/Cu(acac)(2)/ZnI2 were found to be highly reactive and regioselective in the allylic substitution of gamma,gamma-disubstituted secondary allylic picolinates designed for construction of a quaternary carbon, whereas the previous 2:1 ArMgBr/CuBr center dot Me2S reagent and that with ZnX2 were unsuccessful. The generality of the ArMgBr/Cu(acac)(2) reagent was examined with enantiomerically enriched allylic picolinates, which furnished quaternary carbons with high efficiency in >92% regioselectivity and >97% chirality transfer. Two cyclohexanes with a quaternary carbon were synthesized by using these reagents.

  DOI：

  10.1021/jo400248y

文献信息

• Allylic Substitution for Construction of a Chiral Quaternary Carbon Possessing an Aryl Group
  作者：Chao Feng、Yuichi Kobayashi

  DOI：10.1021/jo400248y

  日期：2013.4.19

  Phenylcopper reagents derived from 2:1 PhMgBr/Cu(acac)(2) and 3:1:1 PhMgBr/Cu(acac)(2)/ZnI2 were found to be highly reactive and regioselective in the allylic substitution of gamma,gamma-disubstituted secondary allylic picolinates designed for construction of a quaternary carbon, whereas the previous 2:1 ArMgBr/CuBr center dot Me2S reagent and that with ZnX2 were unsuccessful. The generality of the ArMgBr/Cu(acac)(2) reagent was examined with enantiomerically enriched allylic picolinates, which furnished quaternary carbons with high efficiency in >92% regioselectivity and >97% chirality transfer. Two cyclohexanes with a quaternary carbon were synthesized by using these reagents.
• Construction of quaternary carbon centers by using substitution of γ,γ-disubstituted secondary allylic picolinates with alkylcopper reagents
  作者：Chao Feng、Yuki Kaneko、Yuichi Kobayashi

  DOI：10.1016/j.tetlet.2013.06.046

  日期：2013.8

  ZnI2 was found to promote regio- and stereoselective substitution of gamma,gamma-disubstituted secondary allylic picolinates with alkylcopper reagents derived from alkyl-MgBr and CuBr center dot Me2S in a 2:1 ratio to furnish quaternary carbon centers in good yields. Alkyl groups delivered efficiently were the primary, secondary, and benzyl classes such as Me, Et, Bu, C16H33, Ph(CH2)(2), Ph(CH2)(3), c-C6H11, and Bn. As an application, allylic picolinates with the (E)- or (Z)-olefin afforded quaternary carbon centers that are the enantiomers of each other. (C) 2013 Elsevier Ltd. All rights reserved.