cis-1,4-bis(benzyloxy)-2-cyclohexene | 73977-87-4

• 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: cis-1,4-bis(benzyloxy)-2-cyclohexene
• 英文别名: meso-cis-1,4-Di-O-benzylcyclohex-2-enediol；cis-di-O-benzylcyclohex-2-ene-1,4-diol；[(1S,4R)-4-phenylmethoxycyclohex-2-en-1-yl]oxymethylbenzene
• CAS: 73977-87-4
• 化学式: C₂₀H₂₂O₂
• 分子量: 294.393
• InChiKey: ZAXMYKNEWPZIDZ-BGYRXZFFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-1,4-bis(benzyloxy)-2-cyclohexene 在 lithium trimethylsilylacetylenide 、 氯化二乙基铝 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 120.58h， 生成 1,4-di-O-benzyl-c-3-chlorocyclohexane-r-1,t-2,c-4-triol
  参考文献：
  名称：

  Synthesis of 2,9,10-trioxatricyclo[4.3.1.0]decane analogues of resiniferatoxin

  摘要：

  Structurally simplified analogues of the daphnane diterpene resiniferatoxin (RTX) 1, possessing the unusual 2,9,10-trioxatricyclo[4.3.1.0 3,8]decane system have been synthesised stereoselectively from cyclohexa-1,3-diene: functionalisation of the diene afforded the anti-epoxide, 1,4-di-O-benzyl-t-2,t-3-epoxycyclohexane-r-1,c-4-diol 4, the ring-opening of which was examined using various organometallic reagents; organoaluminium species were found to be the most efficient to effect this reaction. When trimethylsilyl (in place of benzyl) ethers were used to protect the diol, selective deprotection of 1,4-di-O-trimethylsilyl-2-O-(p-tolylsulfonyl)-c-3-[3-(tert-butyldiphenylsilyloxy)-prop-1-ynyl]cyclohexane-r-1,t-2,c-4-triol 16 was achieved using citric acid in methanol - the equatorially disposed trimethylsilyl ether was found to be more easily cleaved than the axially orientated one. Formation of the tricyclic orthoester was achieved by the generation of a dioxolenium ion from 1-O-phenylacetyl-2-O-(p-tolylsulfonyl)-c-3-[3-(tert-butyldiphenylsilyloxy)-prop-1-ynyl]cyclohexane-r-1,t-2,c-4-triol 19, by heating in 2,4,6-trimethylpyridine, with in situ intramolecular trapping by the suitably orientated hydroxy group to give 1-benzyl-7-(3-tert-butyldiphenylsilyloxyprop-1-ynyl)-2,9,10-trioxatricyclo[4.3.1.0 3,8]decane 20.

  DOI：

  10.1039/p19920001229
• 作为产物：
  描述：

  [(cyclohex-2-en-1-yloxy)methyl]benzene 在 溴 、 sodium 作用下， 反应 5.0h， 生成 cis-1,4-bis(benzyloxy)-2-cyclohexene
  参考文献：
  名称：

  Hasegawa, Akira; Kobayshi, Toshiyuki; Kiso, Makoto, Agricultural and Biological Chemistry, 1980, vol. 44, # 1, p. 165 - 168

  摘要：

  DOI：

文献信息

• Desymmetrization of Inert meso-Diethers through Copper-Catalyzed Asymmetric Allylic Alkylation with Grignard Reagents
  作者：Jun Li、Yu Wang、Yan Wang、Lianjie Zhai、Junrong Huang、Lijuan Song、Hengzhi You、Fen-Er Chen

  DOI：10.1021/acs.orglett.4c01972

  日期：2024.7.12

  We have developed a highly regio-, diastereo-, and enantioselective Cu-catalyzed desymmetrization of inert meso-diethers using Grignard reagents. Moreover, previous inaccessible sterically hindered organometallic reagents are realized in the reaction with broad secondary alkyl Grignard reagents. Finally, detailed control experiments and density functional theory calculations revealed the desymmetrization

  我们使用格氏试剂开发了一种高度区域选择性、非对映选择性和对映选择性的铜催化惰性内消旋二醚去对称化反应。此外，以前难以获得的位阻有机金属试剂是在与宽仲烷基格氏试剂的反应中实现的。最后，详细的控制实验和密度泛函理论计算表明，在不存在原位生成的烯丙基溴中间体的情况下，内消旋二醚的去对称化利用了直接的抗-S N 2'途径。接下来的氧化加成是关键的速率决定和对映选择性决定步骤。
• Stereo- and regioselective palladium-catalyzed 1,4-dialkoxylation of conjugated dienes
  作者：Jan E. Baeckvall、Jan O. Vaagberg

  DOI：10.1021/jo00259a016

  日期：1988.11
• BACKVALL, JAN-E.;VAGBERG, JAN O., J. ORG. CHEM., 53,(1988) N 24, C. 5695-5699
  作者：BACKVALL, JAN-E.、VAGBERG, JAN O.

  DOI：——

  日期：——
• Desper, John M.; Gellman, Samuel H., Angewandte Chemie, 1994, vol. 106, # 3, p. 335 - 338
  作者：Desper, John M.、Gellman, Samuel H.

  DOI：——

  日期：——