(1R,2S,4S)-4-(benzyloxymethyl)-1,2-epoxycyclohexane | 163956-42-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1R,2S,4S)-4-(benzyloxymethyl)-1,2-epoxycyclohexane
• 英文别名: (1S,3S,6R)-3-(phenylmethoxymethyl)-7-oxabicyclo[4.1.0]heptane
• CAS: 163956-42-1
• 化学式: C₁₄H₁₈O₂
• 分子量: 218.296
• InChiKey: YVQQRZYUHSWWOK-MJBXVCDLSA-N

物化性质

• 沸点：
  314.2±15.0 °C(Predicted)
• 密度：
  1.086±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  21.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2S,4S)-4-(benzyloxymethyl)-1,2-epoxycyclohexane 在 硫酸 、 sodium hydride 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 18.67h， 生成 c-5-<(benzyloxy)methyl>-t-2-methoxy-r-1-cyclohexanol
  参考文献：
  名称：

  通过螯合方法对1,2-环氧化合物的开环进行区域化学控制。第14部分：在气相操作条件下，与远程O-取代的1,2-环氧环己烷的MeOH进行的开环反应的区域选择性

  摘要：

  使用气态酸（D 3 +，C n H 5 +，Me 2 F +）作为促进剂，在与MeOH进行开环反应的气相中，确定了具有远距离O-官能度的环己烯氧化物的区域化学行为。所获得的结果表明，在缩合相中进行的相应反应（甲烷分解）中完全不存在H +（或D +）介导的螯合双齿物质在气相中的打开过程。

  DOI：

  10.1016/s0040-4020(00)00643-8
• 作为产物：
  描述：

  3-环己烯-1-甲醇 在 吡啶 、 盐酸 、 叔丁基过氧化氢 、 potassium tert-butylate 、 四氯化钛 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醇 、 苯 为溶剂， 反应 13.25h， 生成 (1R,2S,4S)-4-(benzyloxymethyl)-1,2-epoxycyclohexane
  参考文献：
  名称：

  Regiochemical control of the ring-opening of 1,2-epoxides by means of chelating processes. 2. Synthesis and reactions of the cis- and trans-oxides of 4-[(benzyloxy)methyl]cyclohexene, 3-cyclohexenemethanol, and methyl 3-cyclohexenecarboxylate

  摘要：

  The synthesis of the diastereoisomeric epoxides cis-1b-d and trans-2b-d and the products of their ring-opening by various nucleophiles are described. The results of the ring-openings of the trans-epoxides 2b-d can be rationalized by combining stereoelectronic and conformational arguments. However, the regioselectivity of the ring-openings of the cis-epoxides 1b-d can, in principle, be influenced by the chelation of a metal ion by the oxygen atom of the epoxy group and that of the substituent on the 4-position. The results of the reactions of the cis-epoxides 1b-d indicate that, to some degree, chelation is indeed a factor. How important a factor it is is dependent both on the reaction conditions and on the concentration and nature of the metal ion. In the ring-openings of the cis-epoxides 1b and 1d, chelation seems to be a larger factor than it is in the ring-openings of cis-epoxide 1c. However, in no case is chelation as large a factor as it was in the ring-openings of the cis-epoxide 1a, which was studied earlier. On the other hand, the autocatalyzed methanolysis, under neutral conditions, of epoxy acid 1e, followed by CH2N2 methylation of the crude product, afforded a mixture of the two regioisomeric hydroxy ethers in which the C-2-type compound predominates. This result suggests that intramolecular hydrogen bonding may determine the reactive conformation of 1e.

  DOI：

  10.1021/jo00031a018

文献信息

• Regiochemical control of the ring opening of aziridines by means of chelating processes. Part 3: Regioselectivity of the opening reactions with methanol of remote O-substituted regio- and diastereoisomeric activated aziridines under condensed- and gas-phase operating conditions
  作者：Paolo Crotti、Valeria Di Bussolo、Lucilla Favero、Franco Macchia、Gabriele Renzi、Graziella Roselli

  DOI：10.1016/s0040-4020(02)00726-3

  日期：2002.8

  acid methanolysis in the condensed phase (cd-phase) and in the reaction with MeOH in the gas-phase using a gaseous acid (D3+) as the promoting agent. The results obtained in the opening process of the cis diastereoisomers indicate the constant incursion in the gas phase of D+(corresponding to H+)-mediated chelated bidentate species able to modify the regiochemical result found in the methanolysis in

  该非对映异构对活化的氮丙啶的区域化学行为1 - 8从环己烷衍生系统，轴承远程Ó -Functionality，在冷凝相（CD-相）酸甲醇分解被确定并且在该气体中，用MeOH将反应气态酸（D 3 +）作为促进剂的液相。在顺式非对映异构体的打开过程中获得的结果表明，D +（对应于H +）介导的螯合二齿物种在气相中的恒定侵入能够改变cd相在甲醇分解中发现的区域化学结果。
• Stereoselective Transformation of Enantiopure Cyclohexenol into <i>cis</i>-Hydrindan. An Enantioselective Formal Total Synthetic Route to (+)-Pumiliotoxin C
  作者：Masahiro Toyota、Takanobu Asoh、Masaki Matsuura、Keiichiro Fukumoto

  DOI：10.1021/jo9613085

  日期：1996.1.1
• Toyota, Masahiro; Matsuura, Masaki; Fukumoto, Keiichiro, Heterocycles, 1995, vol. 41, # 4, p. 661 - 664
  作者：Toyota, Masahiro、Matsuura, Masaki、Fukumoto, Keiichiro

  DOI：——

  日期：——
• Regiochemical Control of the Ring Opening of 1,2-Epoxides by Means of Chelating Processes. Part 14: Regioselectivity of the Opening Reactions with MeOH of Remote O-Substituted 1,2-Epoxycyclohexanes under Gas-Phase Operating Conditions
  作者：Paolo Crotti、Valeria Di Bussolo、Lucilla Favero、Mauro Pineschi、Francesco Marianucci、Gabriele Renzi、Giuseppina Amici、Graziella Roselli

  DOI：10.1016/s0040-4020(00)00643-8

  日期：2000.9

  was determined in the gas-phase in opening reactions with MeOH, using a gaseous acid (D3+, CnH5+, Me2F+) as the promoting agent. The results obtained indicate the incursion in the opening process in the gas phase of H+(or D+)-mediated chelated bidentate species completely absent in the corresponding reactions (methanolysis) carried out in the condensed phase.

  使用气态酸（D 3 +，C n H 5 +，Me 2 F +）作为促进剂，在与MeOH进行开环反应的气相中，确定了具有远距离O-官能度的环己烯氧化物的区域化学行为。所获得的结果表明，在缩合相中进行的相应反应（甲烷分解）中完全不存在H +（或D +）介导的螯合双齿物质在气相中的打开过程。
• Regiochemical control of the ring-opening of 1,2-epoxides by means of chelating processes. 2. Synthesis and reactions of the cis- and trans-oxides of 4-[(benzyloxy)methyl]cyclohexene, 3-cyclohexenemethanol, and methyl 3-cyclohexenecarboxylate
  作者：Marco Chini、Paolo Crotti、Lee A. Flippin、Franco Macchia、Mauro Pineschi

  DOI：10.1021/jo00031a018

  日期：1992.2

  The synthesis of the diastereoisomeric epoxides cis-1b-d and trans-2b-d and the products of their ring-opening by various nucleophiles are described. The results of the ring-openings of the trans-epoxides 2b-d can be rationalized by combining stereoelectronic and conformational arguments. However, the regioselectivity of the ring-openings of the cis-epoxides 1b-d can, in principle, be influenced by the chelation of a metal ion by the oxygen atom of the epoxy group and that of the substituent on the 4-position. The results of the reactions of the cis-epoxides 1b-d indicate that, to some degree, chelation is indeed a factor. How important a factor it is is dependent both on the reaction conditions and on the concentration and nature of the metal ion. In the ring-openings of the cis-epoxides 1b and 1d, chelation seems to be a larger factor than it is in the ring-openings of cis-epoxide 1c. However, in no case is chelation as large a factor as it was in the ring-openings of the cis-epoxide 1a, which was studied earlier. On the other hand, the autocatalyzed methanolysis, under neutral conditions, of epoxy acid 1e, followed by CH2N2 methylation of the crude product, afforded a mixture of the two regioisomeric hydroxy ethers in which the C-2-type compound predominates. This result suggests that intramolecular hydrogen bonding may determine the reactive conformation of 1e.