trans-(9R,10R)-9-Azido-10-hydroxy-9,10-dihydrophenanthrene | 146141-56-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: trans-(9R,10R)-9-Azido-10-hydroxy-9,10-dihydrophenanthrene
• 英文别名: trans-10-Azido-9,10-dihydrophenanthrar-9-ol；9-Phenanthrenol, 10-azido-9,10-dihydro-, trans-；(9R,10R)-10-azido-9,10-dihydrophenanthren-9-ol
• CAS: 146141-56-2
• 化学式: C₁₄H₁₁N₃O
• 分子量: 237.261
• InChiKey: BBWLKNHCRZAQMC-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  34.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  trans-(9R,10R)-9-Azido-10-hydroxy-9,10-dihydrophenanthrene 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以89%的产率得到trans-(9R,10R)-9-Amino-10-hydroxy-9,10-dihydrophenanthrene
  参考文献：
  名称：

  Synthesis and Assignment of Absolute Configuration to the N6-Deoxyadenosine Adducts Resulting from Cis and Trans Ring-Opening of Phenanthrene 9,10-Oxide

  摘要：

  Reaction of calf thymus DNA with phenanthrene 9,10-oxide in vitro results in alkylation of the exocyclic amino groups of the purine bases. Adducts result from both cis and trans opening of the epoxide. In the present study, structures of the N-6-deoxyadenosine adducts have been unequivocally assigned by synthesis from optically pure cis- and trans-9-amino-10-hydroxy-9,10-dihydrophethrene. Resolution of trans-9-azido-10-hydroxy-9,10-dihydrophenanthrene as its acetate was achieved on a chiral. HPLC column. The early-eluting (-)-enantiomer was assigned (9R,10R)-absolute configuration based on a characteristic negative CD band at 232 nm due to the helicity of its biphenyl chromophore, in combination with a H-1 NMR coupling constant that indicated pseudodiaxial orientation of the substituents at C-9 and C-10. Aminolysis of the ester followed by reduction of the azido group provided the desired, optically active trans (9R,10R) amino alcohol. As a starting material for synthesis of the cis amino alcohol, trans-9-bromo-10-acetoxy-9,10-dihydrophe was resolved by chiral HPLC. As above, the early-eluting (-)-enantiomer was assigned (9R,10R)absolute configuration based on a characteristic negative CD band at 234 nm. Displacement of bromine with inversion of configuration by azide, aminolysis of the ester, and reduction provided optically pure cis-(9S,10R)-9-amino-10-hydroxy-9,10-dihydrophenanthrene. Coupling of the optically active amino alcohols with 6-fluoro-9-(2-deoxy-beta-D-erythro-pentofuranosyl) purine (the 6-fluoro analog of dA) yielded the corresponding N-6-deoxyadenosine adducts. Comparison of CD spectra and HPLC retention times of the synthetic adducts with those of the adducts obtained from calf thymus DNA make it possible to assign unambiguously the structures of the DNA adducts.

  DOI：

  10.1021/jo00086a027
• 作为产物：
  描述：

  9,10-环氧-9,10-二氢菲 在 吡啶 、 sodium azide 、 18-冠醚-6 、 叠氮基三甲基硅烷 、 氨 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 3.25h， 生成 trans-(9R,10R)-9-Azido-10-hydroxy-9,10-dihydrophenanthrene
  参考文献：
  名称：

  Synthesis and Assignment of Absolute Configuration to the N6-Deoxyadenosine Adducts Resulting from Cis and Trans Ring-Opening of Phenanthrene 9,10-Oxide

  摘要：

  Reaction of calf thymus DNA with phenanthrene 9,10-oxide in vitro results in alkylation of the exocyclic amino groups of the purine bases. Adducts result from both cis and trans opening of the epoxide. In the present study, structures of the N-6-deoxyadenosine adducts have been unequivocally assigned by synthesis from optically pure cis- and trans-9-amino-10-hydroxy-9,10-dihydrophethrene. Resolution of trans-9-azido-10-hydroxy-9,10-dihydrophenanthrene as its acetate was achieved on a chiral. HPLC column. The early-eluting (-)-enantiomer was assigned (9R,10R)-absolute configuration based on a characteristic negative CD band at 232 nm due to the helicity of its biphenyl chromophore, in combination with a H-1 NMR coupling constant that indicated pseudodiaxial orientation of the substituents at C-9 and C-10. Aminolysis of the ester followed by reduction of the azido group provided the desired, optically active trans (9R,10R) amino alcohol. As a starting material for synthesis of the cis amino alcohol, trans-9-bromo-10-acetoxy-9,10-dihydrophe was resolved by chiral HPLC. As above, the early-eluting (-)-enantiomer was assigned (9R,10R)absolute configuration based on a characteristic negative CD band at 234 nm. Displacement of bromine with inversion of configuration by azide, aminolysis of the ester, and reduction provided optically pure cis-(9S,10R)-9-amino-10-hydroxy-9,10-dihydrophenanthrene. Coupling of the optically active amino alcohols with 6-fluoro-9-(2-deoxy-beta-D-erythro-pentofuranosyl) purine (the 6-fluoro analog of dA) yielded the corresponding N-6-deoxyadenosine adducts. Comparison of CD spectra and HPLC retention times of the synthetic adducts with those of the adducts obtained from calf thymus DNA make it possible to assign unambiguously the structures of the DNA adducts.

  DOI：

  10.1021/jo00086a027

文献信息

• WEITZBERG M.; AIZENSHTAT Z.; JERUSHALMY P.; BLUM J., J. ORG. CHEM., 1980, 45, NO 21, 4252-4254
  作者：WEITZBERG M.、 AIZENSHTAT Z.、 JERUSHALMY P.、 BLUM J.

  DOI：——

  日期：——
• Exl Christina, Hoenig Helmut, Renner Gerald, Rogi-Kohlenprath Renate, See+, Tetrahedron: Asymmetry, 3 (1992) N 11, S 1391-1394
  作者：Exl Christina, Hoenig Helmut, Renner Gerald, Rogi-Kohlenprath Renate, See+

  DOI：——

  日期：——
• WEITZBERG, M.;AVNIR, D.;AIZENSHTAT, Z.;BLUM, J., J. HETEROCYCL. CHEM., 1983, 20, N 4, 1019-1022
  作者：WEITZBERG, M.、AVNIR, D.、AIZENSHTAT, Z.、BLUM, J.

  DOI：——

  日期：——
• WEITZBERG, M.;AIZENSHTAT, Z.;BLUM, J., J. HETEROCYCL. CHEM., 1985, 22, N 3, 865-868
  作者：WEITZBERG, M.、AIZENSHTAT, Z.、BLUM, J.

  DOI：——

  日期：——
• SHUDO K.; OKAMOTO T., CHEM. AND PHARM. BULL. <CPBT-AL>, 1976, 24, NO 5, 1013-1015
  作者：SHUDO K.、 OKAMOTO T.

  DOI：——

  日期：——