(-)-(1R,2S,4S)-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-yl acetate | 894806-69-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(1R,2S,4S)-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-yl acetate
• 英文别名: [(1R,2S,4S)-1,4,5,6-tetrachloro-7,7-dimethoxy-2-bicyclo[2.2.1]hept-5-enyl] acetate
• CAS: 894806-69-0
• 化学式: C₁₁H₁₂Cl₄O₄
• 分子量: 350.026
• InChiKey: FFSXDNVDSRAIPV-QUNWWBBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (-)-(1R,2S,4S)-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-yl acetate 在 lead(IV) acetate 、 ruthenium trichloride 、 indium 、 sodium tetrahydroborate 、 sodium periodate 、 氯化铵 作用下， 以 甲醇 、 乙腈 、 苯 为溶剂， 反应 35.67h， 生成
  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：

  5,5-二甲氧基-1,2,3,4-四氯环戊二烯 在 4-二甲氨基吡啶 作用下， 反应 168.0h， 生成 (-)-(1R,2S,4S)-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-en-2-yl 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

文献信息

• 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。