[(Z,3S)-1-cyclohexyl-6-[(4-methoxyphenyl)methoxy]hex-1-en-3-yl] pyridine-2-carboxylate | 1094860-73-7

• 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: [(Z,3S)-1-cyclohexyl-6-[(4-methoxyphenyl)methoxy]hex-1-en-3-yl] pyridine-2-carboxylate
• CAS: 1094860-73-7
• 化学式: C₂₆H₃₃NO₄
• 分子量: 423.552
• InChiKey: ZMCGCGCHPUFMPG-CZKPLACNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  31
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  57.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [(Z,3S)-1-cyclohexyl-6-[(4-methoxyphenyl)methoxy]hex-1-en-3-yl] pyridine-2-carboxylate 、 苯基锂 在 溴化亚铜二甲硫醚 、 magnesium bromide 作用下， 以 四氢呋喃 、 乙醚 、 环己烷 为溶剂， 反应 0.5h， 以94%的产率得到(R,E)-1-cyclohexyl-6-((4-methoxybenzyl)oxy)-1-phenylhex-2-ene
  参考文献：
  名称：

  用有机锂衍生的芳基和烯基铜试剂进行烯丙基取代的新方案

  摘要：

  建立了由sp 2-碳锂和CuBr·Me 2 S衍生的铜试剂取代烯丙基吡啶啉酸酯，以提供具有几乎完美的区域选择性和手性转移的抗S N 2'产物。将有机锂的制备方法（例如锂-卤素交换和邻位锂化）与取代反应相结合，以安装各种sp 2-碳基团，其中包括Ph，2,6-Me 2 C 6 H 3，4 -Me-2,6- （MOMO）C 6 H 2，以及顺式和反式1-庚烯基。

  DOI：

  10.1016/j.tetlet.2008.10.002
• 作为产物：
  描述：

  (S)-1-cyclohexyl-6-[(4-methoxybenzyl)oxy]-1-hexyn-3-yl pyridine-2-carboxylate 在 Lindlar's catalyst 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 48.0h， 以86%的产率得到[(Z,3S)-1-cyclohexyl-6-[(4-methoxyphenyl)methoxy]hex-1-en-3-yl] pyridine-2-carboxylate
  参考文献：
  名称：

  Formation of Chiral C(sp³)−C(sp) Bond by Allylic Substitution of Secondary Allylic Picolinates and Alkynyl Copper Reagents

  摘要：

  To establish allylic substitution of secondary allylic alcohol derivatives with alkynyl copper reagents, allylic esters bearing the (2-pyridine)CO2-, (2-pyrazine)CO2-, (EtO)(2)PO2-, C6F5CO2-, o-(Ph2P)-C6H4CO2-, MeOCO2-, or AcO-group were examined. First, picolinate (R-1 = Me, R-2 = CH2OPMB) was subjected to reaction with (TMS-C C)(2)CuLi center dot LiBr at 0 degrees C. Although no substitution took place, MgBr, (3 equiv) was found to promote the reaction to produce the anti S(N)2' product in 93% yield with 94% regioselectivity and 99% chirality transfer. In contrast, substitution of the other esters with the copper reagent in the presence of MgBr, were less reactive ((2-pyrazin)CO2-) or marginally reactive (other cases). Generality of the substitution using picolinates was established with five picolinates (R-1 = Me, Ph(CH2)(2), PMBO(CH2)(3); R-2 = Me, CH2OPMB, CH2OTBS, C5H11, c-C6H11) and seven alkynyl copper reagents (R-3 = TMS, Ph, p-TBSOC6H4, p- and o-MeOC6H4, P-MeC6H4, p-FC6H4), furnishing anti S(N)2' products in 61-93% yields with high regioselectivity (usually > 90%) and high chirality transfer (usually > 95%). In addition, transformation of the products was briefly studied.

  DOI：

  10.1021/jo901728b

文献信息

• Highly efficient substitution of allylic picolinates with copper reagents derived from aryl-, alkenyl-, furyl-, and thienyl-lithiums
  作者：Yohei Kiyotsuka、Yuichi Kobayashi

  DOI：10.1016/j.tet.2009.11.052

  日期：2010.1

  R2=CH2OTBS), with phenylcopper reagents derived from salt free PhLi (2 equiv) and CuBr·Me2S (2 and 1 equiv, respectively) was highly promoted by MgBr2 (3 equiv), producing anti SN2′ product regio- and stereoselectively. This reagent system was proven to be general with several picolinates (R1, R2: Ph(CH2)2, PMBO(CH2)3, Me, TBSOCH2, PMBOCH2, c-Hex). Furthermore, aryl copper reagents prepared from ArLi, which

  用衍生自苯基铜的试剂取代光学活性的烯丙基吡啶甲酸顺式R 1 -CH（OC（O）（2-Py））CH CHR 2（R 1 =（CH 2）2 Ph，R 2 = CH 2 OTBS）MgBr 2（3当量）高度促进了无盐PhLi（2当量）和CuBr·Me 2 S（分别为2和1当量），产生区域和立体选择性的抗S N 2'产物。事实证明，该试剂体系与几种吡啶甲酸（R 1，R 2：Ph（CH 2）2，PMBO（CH）2）3，Me，TBSOCH 2，PMBOCH 2，c -Hex）。此外，事实证明，由ArLi制备的芳基铜试剂可通过锂-卤素交换制得，与存在的MgBr 2交换量比交换产生的LiX量大的MgBr 2兼容。2-MeOC：取代不与芳基上铜板（Ar'的空间位阻干扰6 ħ 4，2,6-（MOMO）2 -4-MEC 6 ħ 2，2,6-ME 2 ç 6 ħ 3等）。同样，立体定义的顺式和反式烯基，呋喃基和噻吩基试剂可有效地产生相应的抗S
• Formation of Chiral C(sp³)−C(sp) Bond by Allylic Substitution of Secondary Allylic Picolinates and Alkynyl Copper Reagents
  作者：Yohei Kiyotsuka、Yuichi Kobayashi

  DOI：10.1021/jo901728b

  日期：2009.10.2

  To establish allylic substitution of secondary allylic alcohol derivatives with alkynyl copper reagents, allylic esters bearing the (2-pyridine)CO2-, (2-pyrazine)CO2-, (EtO)(2)PO2-, C6F5CO2-, o-(Ph2P)-C6H4CO2-, MeOCO2-, or AcO-group were examined. First, picolinate (R-1 = Me, R-2 = CH2OPMB) was subjected to reaction with (TMS-C C)(2)CuLi center dot LiBr at 0 degrees C. Although no substitution took place, MgBr, (3 equiv) was found to promote the reaction to produce the anti S(N)2' product in 93% yield with 94% regioselectivity and 99% chirality transfer. In contrast, substitution of the other esters with the copper reagent in the presence of MgBr, were less reactive ((2-pyrazin)CO2-) or marginally reactive (other cases). Generality of the substitution using picolinates was established with five picolinates (R-1 = Me, Ph(CH2)(2), PMBO(CH2)(3); R-2 = Me, CH2OPMB, CH2OTBS, C5H11, c-C6H11) and seven alkynyl copper reagents (R-3 = TMS, Ph, p-TBSOC6H4, p- and o-MeOC6H4, P-MeC6H4, p-FC6H4), furnishing anti S(N)2' products in 61-93% yields with high regioselectivity (usually > 90%) and high chirality transfer (usually > 95%). In addition, transformation of the products was briefly studied.
• New protocol for allylic substitution with aryl and alkenyl copper reagents derived from organolithiums
  作者：Yohei Kiyotsuka、Yuichi Kobayashi

  DOI：10.1016/j.tetlet.2008.10.002

  日期：2008.12

  Substitution of allylic picolinoates with copper reagents derived from sp2-carbon-lithiums and CuBr·Me2S was established to furnish anti SN2′ products with almost perfect regioselectivity and chirality transfer. The preparations of organolithiums such as lithium–halogen exchange and ortho lithiation were coupled to the substitution to install various sp2-carbon groups, which include Ph, 2,6-Me2C6H3

  建立了由sp 2-碳锂和CuBr·Me 2 S衍生的铜试剂取代烯丙基吡啶啉酸酯，以提供具有几乎完美的区域选择性和手性转移的抗S N 2'产物。将有机锂的制备方法（例如锂-卤素交换和邻位锂化）与取代反应相结合，以安装各种sp 2-碳基团，其中包括Ph，2,6-Me 2 C 6 H 3，4 -Me-2,6- （MOMO）C 6 H 2，以及顺式和反式1-庚烯基。