(1RS,2SR,4SR)-7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo<2.2.1>hept-5-en-2-ol | 90254-09-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1RS,2SR,4SR)-7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo<2.2.1>hept-5-en-2-ol
• 英文别名: (+/-)-(1R,2S,4S)-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-ol；7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo<2.2.1>hept-5-en-2-ol；1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-ol；7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo[2.2.1]hept-5-en-2-ol；(1R,2S,4S)-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-ol
• CAS: 90254-09-4；112460-47-6；133962-63-7
• 化学式: C₉H₁₀Cl₄O₃
• 分子量: 307.989
• InChiKey: YNCWCLKRNPEETQ-NETWJXFUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1RS,2SR,4SR)-7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo<2.2.1>hept-5-en-2-ol 在 4-二甲氨基吡啶 、 ruthenium trichloride 、 indium 、 sodium periodate 、 氯化铵 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 23.17h， 生成 [(1S,2S,4R,5S)-1,4-dichloro-5-hydroxy-7,7-dimethoxy-6-oxo-2-bicyclo[2.2.1]heptanyl] acetate
  参考文献：
  名称：

  Unexpected formation of a chiral δ-lactone by reduction of the 1,3-dicarbonylic cyclopentanoid derivatives

  摘要：

  We have described the synthesis of highly functionalized chiral cyclopentanoids, which are important building units for synthesis of biological active compounds. The (-)- or (+)-7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo[2.2.1]hept-5-en-2-endo-yl acetate, obtained from the enzyme catalyzed transesterification of the racemate, was converted to alpha-diketone chiral. The alpha-diketone was treated with H2O2/NaOH and esterified with CH2N2 to furnish a mixture of the compounds (+)- or (-)-10 and (+)- or (-)-11. The reduction of the (+)- or (-)-10 and/or (+)- or (-)-11 with BH3 center dot THF furnished the lactone (+)- or (-)-13 with excellent yield. The alpha-diketone was reduced with indium metal in the presence of NH4Cl furnishing the acyloin (+)-14 in 67%, of yield. The treatment of acyloin (+)-14 with Pb(OAc)(4) furnished the aldehyde (+)-15 with 80% of yield. The reduction of the aldehyde (+)-15 with NaBH4 has again produced the lactone (+)-13. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.03.062
• 作为产物：
  描述：

  (+/-)-(1R,2S,4S)-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-yl acetate 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 0.33h， 以100%的产率得到(1RS,2SR,4SR)-7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo<2.2.1>hept-5-en-2-ol
  参考文献：
  名称：

  Synthetic studies related to CP-225,917

  摘要：

  与CP-225,917相关的合成研究被描述，包括制备完全氧化的四环中心核心3。关键词：CP-225,917，硅氧-Cope重排，Cope重排，应变辅助重排，呋喃，二氧化钌，桥头烯。

  DOI：

  10.1139/v03-086

文献信息

• Rearrangement of 1,4,5,6-tetrahalo-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-ones to phenolic derivatives
  作者：Faiz Ahmed Khan、Jyotirmayee Dash、Dheeraj Jain、B. Prabhudas

  DOI：10.1039/b108152g

  日期：2001.11.29

  A simple Diels–Alder route leading to methyl 2,3,4-trihalo-5-hydroxybenzoates via thermal Grob-type rearrangement of easily accessible 1,4,5,6-tetrahalo-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-one with concomitant methyl halide elimination is described.

  一种简单的Diels-Alder路线，可通过容易获得的1,4,5,6-四卤代7,7-二甲氧基双环[2.2.1]的热Grob型重排产生2,3,4-三卤代-5-羟基苯甲酸甲酯-5-en-2-一个伴随卤代甲烷 描述消除。
• Robust synthesis of enantiopure cyclohexenyl analogues of 2/3-deoxyribose sugars as carbocyclic nucleoside precursors
  作者：Manojkumar Varada、Venubabu Kotikam、Vaijayanti A. Kumar

  DOI：10.1016/j.tet.2011.06.003

  日期：2011.8

  An expedient synthesis of 2-deoxy (10) and 3-deoxy (11) cyclohexenyl analogues of 2-deoxy and 3-deoxy-d-ribose sugar from commercially available starting materials is reported. Highly efficient enzymatic resolution of the key compound 10 is described using lipase under hydrolytic conditions. The robust methodology applied here will be useful to synthesize cyclohexenyl nucleosides, which possess potent

  2-脱氧（的一个适宜的合成10）和3-脱氧（11）2-脱氧和3-脱氧的环己烯基类似物d报道从市售的起始原料-核糖的糖。在水解条件下使用脂肪酶描述了关键化合物10的高效酶促拆分。此处应用的可靠方法学将对合成具有有效抗病毒活性并能够通过RNAi或反义应用进行基因沉默的环己烯基核苷有用。
• An unusual occurrence of chemiluminescence resulting from metal–ammonia reductive dehalogenation reactions
  作者：Evangelo Cotsaris、Michael N. Paddon-Row

  DOI：10.1039/c39840000095

  日期：——

  Birch type reductive dehalogenation of some member of the series of norbornenes (2a–h), (4i) proceeds with chemiluminescence; an explanation for this phenomenon is advanced.

  降冰片烯系列（2a – h），（4i）系列中的某些成员的桦木型还原脱卤作用随着化学发光的进行；对此现象的解释已经提出。
• New Efficient Route to the Synthesis of Enantiopure (+) and (−) Bicyclo[2.2.1]heptan‐<i>syn</i>‐2,7‐diol using Lipase‐Catalyzed Transesterifications
  作者：José E. D. Martins、Luciane F. de Oliveira、Valentim E. U. Costa

  DOI：10.1080/00397910600941489

  日期：2006.11.1

  [2.2.1]hept‐5‐en‐2‐endo‐ol (±)‐7, using lipase‐catalyzed transesterification and a series of standard procedures, we prepared the enantiomers (+)‐(2R, 7S) and (−)‐(2S, 7R) bicyclo[2.2.1] heptan‐2,7‐syn‐diol 3 through a new alternative route with excellent yields and enantiomeric excess (up to 99%). These chiral bidentate compounds possess very rigid molecular structures and a favorable stereochemistry

  摘要 从外消旋的 7,7-二甲氧基-1,4,5,6-四氯双环[2.2.1]hept-5-en-2-endo-ol (±)-7 开始，使用脂肪酶催化的酯交换和一系列按照标准程序，我们通过新的替代路线制备了对映异构体 (+)-(2R, 7S) 和 (-)-(2S, 7R) bicyclo[2.2.1] heptan-2,7-syn-diol 3和对映体过量（高达 99%）。这些手性双齿化合物具有非常刚性的分子结构和有利的金属配位立体化学，因此成为不对称合成的有前途的手性配体。
• Murthy, Y V S Narayana; Pillai, C N, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1992, vol. 31, # 11, p. 796 - 798
  作者：Murthy, Y V S Narayana、Pillai, C N

  DOI：——

  日期：——