1-carbomethoxy-5-hydro-cyclohexene | 85576-03-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-carbomethoxy-5-hydro-cyclohexene
• 英文别名: Methyl 5-hydroxy-1-cyclohexenecarboxylate；Methyl 5-hydroxy-1-cyclohexene-1-carboxylate；methyl 5-hydroxycyclohexene-1-carboxylate
• CAS: 85576-03-0
• 化学式: C₈H₁₂O₃
• 分子量: 156.181
• InChiKey: LJZHDEMRLUGVDX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-carbomethoxy-5-hydro-cyclohexene 在 manganese(IV) oxide 、 calcium sulfate 、 二异丁基氢化铝 、 silver(l) oxide 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 苯 为溶剂， 反应 212.0h， 生成 (1S,2R,6R,8aR)/(1R,2S,6S,8aS)-1,2,3,5,6,7,8,8a-Octahydro-6-methoxy-N-phenyl-1,2-naphthalenedicarboximide
  参考文献：
  名称：

  Diastereofacial selectivity of Diels-Alder reactions of carbohydrate-derived dienes and their carbocyclic analogs

  摘要：

  The Diels-Alder reactions of two dienes derived from carbohydrates and their carbocyclic analogs are described. The dienes (2S)-3,4-dihydro-2-methoxy-6-vinyl-2H-pyran (1) and (4R)-3,4-dihydro-4-methoxy-6-vinyl-2H-pyran(2) were synthesized from tri-O-acetyl-D-glucal. Cycloaddition reactions of these dienes, each of which contains a single methoxy group at either the allylic or anomeric position, were carried out with a series of dienophiles including N-phenylmaleimide, dimethyl acetylenedicarboxylate, diethyl azodicarboxylate, and N-phenyl-1,2,4-triazoline-3,5-dione. The incorporation of an amine base in the Diels-Alder reactions was found to be essential for the formation of good yields of unrearranged cycloadducts. Structures of the cycloadducts were assigned using NMR methods and X-ray crystallographic analysis. The diastereofacial selectivities observed for dienes 1 and 2 are compared with those of the analogous carbocyclic dienes 3 and 4, the former of which was synthesized for this study from m-anisic acid. Cycloadditions to both the carbohydrate-derived dienes and their carbocyclic analogs were found to occur with a preference for addition of the dienophile to the face of the diene opposite the methoxyl group in every case. The degree of stereoselectivity was sensitive to a number of factors including the location of the substituents attached to the ring of the semicyclic diene, the presence of oxygen in the ring, and the type of dienophile. The dominant trend for anti addition in the Diels-Alder reactions is discussed in terms of diene conformation and secondary orbital effects in the transition state for cycloaddition.

  DOI：

  10.1021/jo00070a039
• 作为产物：
  描述：

  methyl 7-oxabicyclo<2.2.1>heptane-2-carboxylate 在 氯化铵 、 lithium hexamethyldisilazane 作用下， 生成 1-carbomethoxy-5-hydro-cyclohexene
  参考文献：
  名称：

  路易斯酸催化呋喃的狄尔斯-阿尔德反应。取代的环己醇和环己烯醇的区域和立体定向合成。

  摘要：

  在存在路易斯酸（即ZnI 2）的情况下，呋喃和一些亲二烯体之间的[4 + 2]环加成反应可以大大加速。7-氧杂双环[2.2.1]庚基系统容易进行碱促进的β-消除。杂原子桥导致取代的环己醇和环己烯醇。

  DOI：

  10.1016/s0040-4039(00)85823-2

文献信息

• On the lewis acid catalyzed diels-alder reaction of furan. regio- and stereospecific synthesis of substituted cyclohexenols and cyclohexadienols.
  作者：Francis Brion

  DOI：10.1016/s0040-4039(00)85823-2

  日期：1982.1

  The [4+2] cycloaddition between furan and some dienophiles can be greatly accelerated in the presence of a Lewis-Acid (i.e. ZnI2. The 7-oxabicyclo [2.2.1] heptyl system readily undergoes a base promoted β-elimination of the heteroatom bridge leading to substituted cyclohexenols and cyclohexadienols.

  在存在路易斯酸（即ZnI 2）的情况下，呋喃和一些亲二烯体之间的[4 + 2]环加成反应可以大大加速。7-氧杂双环[2.2.1]庚基系统容易进行碱促进的β-消除。杂原子桥导致取代的环己醇和环己烯醇。
• BRION, F., TETRAHEDRON LETT., 1982, 23, N 50, 5299-5302
  作者：BRION, F.

  DOI：——

  日期：——
• [EN] BIOREACHABLE CHIRAL DOPANTS FOR LIQUID CRYSTAL APPLICATIONS<br/>[FR] DOPANTS CHIRAUX "BIOATTEIGNABLES" POUR DES APPLICATIONS DE CRISTAUX LIQUIDES
  申请人：ZYMERGEN INC

  公开号：WO2020159620A9

  公开（公告）日：2020-10-22

  [EN] The disclosure discusses chiral dopants for liquid-crystalline materials. Chiral dopants can be bioreachable compounds, i.e., compounds produced from microbes through fermentation. Chiral dopants can also include bioreachable materials that are further modified by chemical synthetic steps. Chiral dopants as discussed herein can include biomolecules such as glycyrrhetinic acid (1), S-narigenin (2), shikimic acid (3), alpha-phellandrene (4), betulin (5), malic acid (6), valencene (7), or nootkatone (8), and any stereoisomers or chemically modified derivatives thereof. The disclosure further shows optical properties of such compounds in a liquid-crystalline material.
  [FR] La divulgation présente des dopants chiraux pour des matières cristallines liquides. Les dopants chiraux peuvent être des composés "bioatteignables", c'est-à-dire des composés produits à partir de microbes par fermentation. Les dopants chiraux peuvent également comprendre des matières "bioatteignables" qui sont encore modifiées par des étapes synthétiques chimiques. Les dopants chiraux selon l'invention peuvent comprendre des biomolécules telles que l'acide glycyrrhétinique (1), la S-narigénine (2), l'acide shikimique (3), l'alpha-phellandrène (4), la bétuline (5), l'acide malique (6), le valencène (7), ou le nootkatone (8), et tout stéréo-isomère ou ses dérivés chimiquement modifiés. La divulgation présente en outre les propriétés optiques de tels composés dans une matière cristalline liquide.
• Keay, B. A.; Rajapaksa, D; Rodrigo, R., Canadian Journal of Chemistry, 1984, vol. 62, p. 1093 - 1098
  作者：Keay, B. A.、Rajapaksa, D、Rodrigo, R.

  DOI：——

  日期：——
• Diastereofacial selectivity of Diels-Alder reactions of carbohydrate-derived dienes and their carbocyclic analogs
  作者：Robert M. Giuliano、Alfonzo D. Jordan、A. Diane Gauthier、Karst Hoogsteen

  DOI：10.1021/jo00070a039

  日期：1993.8

  The Diels-Alder reactions of two dienes derived from carbohydrates and their carbocyclic analogs are described. The dienes (2S)-3,4-dihydro-2-methoxy-6-vinyl-2H-pyran (1) and (4R)-3,4-dihydro-4-methoxy-6-vinyl-2H-pyran(2) were synthesized from tri-O-acetyl-D-glucal. Cycloaddition reactions of these dienes, each of which contains a single methoxy group at either the allylic or anomeric position, were carried out with a series of dienophiles including N-phenylmaleimide, dimethyl acetylenedicarboxylate, diethyl azodicarboxylate, and N-phenyl-1,2,4-triazoline-3,5-dione. The incorporation of an amine base in the Diels-Alder reactions was found to be essential for the formation of good yields of unrearranged cycloadducts. Structures of the cycloadducts were assigned using NMR methods and X-ray crystallographic analysis. The diastereofacial selectivities observed for dienes 1 and 2 are compared with those of the analogous carbocyclic dienes 3 and 4, the former of which was synthesized for this study from m-anisic acid. Cycloadditions to both the carbohydrate-derived dienes and their carbocyclic analogs were found to occur with a preference for addition of the dienophile to the face of the diene opposite the methoxyl group in every case. The degree of stereoselectivity was sensitive to a number of factors including the location of the substituents attached to the ring of the semicyclic diene, the presence of oxygen in the ring, and the type of dienophile. The dominant trend for anti addition in the Diels-Alder reactions is discussed in terms of diene conformation and secondary orbital effects in the transition state for cycloaddition.