(+/-)-syn-dibenzo[a,l]pyrene 11,12-dihydrodiol 13,14-epoxide | 153857-28-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: (+/-)-syn-dibenzo[a,l]pyrene 11,12-dihydrodiol 13,14-epoxide
• 英文别名: 11,12-Dihydroxy-13,14-epoxy-11,12,13,14-tetrahydrodibenzo(a,l)pyrene；(3S,5R,6S,7R)-4-oxaheptacyclo[11.10.2.02,8.03,5.010,24.017,25.018,23]pentacosa-1(24),2(8),9,11,13(25),14,16,18,20,22-decaene-6,7-diol
• CAS: 153857-28-4
• 化学式: C₂₄H₁₆O₃
• 分子量: 352.389
• InChiKey: CJAMAUFDXDSQLU-NAVOZUGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  27
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  53
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2'-脱氧鸟苷 、 (+/-)-syn-dibenzo[a,l]pyrene 11,12-dihydrodiol 13,14-epoxide 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以59%的产率得到(+/-)-syn-11,12,13-trihydroxy-14-N7guanine-11,12,13,14-tetrahydro-dibenzo[a,l]pyrene
  参考文献：
  名称：

  Structure Elucidation of the Adducts Formed by Fjord Region Dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-Epoxides with Deoxyguanosine

  摘要：

  (+/-)-anti-Dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-epoxide {(+/-)-anti-DB[a,l]PDE} was reacted with deoxyguanosine (dG) in dimethylformamide at 100 degrees C for 30 min, and two sets of adducts were isolated: a mixture of (+/-)-anti-cis- & -trans-N(2)dG (43%) and a mixture of (+/-)-anti-cis- & -trans-N7Gua (45%). Both are mixtures of four stereoisomers that cannot be separated by HPLC. Similarly, (+/-)-syn-DB[a,l]PDE was reacted with dG under the same conditions, and (+/-)-syn-cis- & -trans-N(2)dG (38%) and (+/-)-syn-cis- & -trans-N7Gua (59%) were obtained. The structures of the adducts were determined by a combination of NMR and fast atom bombardment mass spectrometry. By reacting (-)-anti-DB[a,l]PDE or (+)-syn-DB[a,l]PDE with dG under the same conditions, however, optically pure N(2)dG and N7Gua isomers were obtained: (-)-anti-cis-N(2)dG (12%), (-)-anti-trans-N(2)dG (17%), (-)-anti-trans-N7Gua (43%), (+)-syn-cis-N(2)dG (7%), (+)-syn-trans-N(2)dG (3%), (+)-syn-cis-N7Gua (36%), and (+)-syn-trans-N7Gua (22%). The structures of the optically pure adducts were assigned by NMR. syn- and anti-DB[a,l]PDE-N(2)dG adducts can be distinguished by fluorescence line-narrowing spectroscopy (FLNS). Moreover, distinction between cis- and trans-stereochemistry of the adducts is also straightforward by FLNS, because the FLN spectra for the four DB[a,l]PDE-N(2)dG adducts, anti-cis, anti-trans, syn-cis, and syn-trans, are spectroscopically unique.

  DOI：

  10.1021/tx980234k

文献信息

• Spectral and Conformational Analysis of Deoxyadenosine Adducts Derived from <i>syn- </i>and <i>anti</i>-Dibenzo[<i>a</i>,<i>l</i>]pyrene Diol Epoxides: Fluorescence Studies
  作者：Ryszard Jankowiak、Cheng-Huang Lin、Dan Zamzow、Kenneth P. Roberts、Kai-Ming Li、Gerald J. Small

  DOI：10.1021/tx980233s

  日期：1999.9.1

  a half-chair structure in the cyclohexenyl ring, but a deviation from planarity in the fjord region different from that of conformer II of cis-anti-DB[a, l]PDE-N(6)dA. This new structure is labeled as conformer II'. Its (0, 0) fluorescence band is at 388.1 and 388.3 nm in ethanol and glycerol/water glasses, respectively, consistent with the folded-type configuration revealed by the calculations. The

  反式-顺式，顺式-顺式，反式-反式和顺式-二苯并[a，l] py二醇环氧（DB [a，l] PDE）-的低温荧光光谱和构象研究结果给出了衍生的脱氧腺苷（dA）加合物，并将其与先前获得的立体异构DB [a，l] P四醇[Jankowiak，R.等人。（1997）Chem。Res。毒药。10，677-686]。与仅反式异构体表现出两个构象的DB [a，l] P四元醇相反，所有立体异构体dA加合物采用两种不同的构象，环己烯基环具有半椅或半船结构，并且带有一个“开放”- dA和DB [a，1] P部分之间的“折叠”型构型。反式-顺式，顺式-顺式和反式-DB [a，可根据先前对DB [a，l] P四元醇的计算分配l] PDE-14-N（6）dA。反式-顺式-顺式-DB-DB [a，l] PDE-14-N（6）dA加合物的主要构象物存在于构象I和II中，其荧光起源带在大约382和大约389 nm处，分
• Structure Elucidation of the Adducts Formed by Fjord-Region Dibenzo[<i>a</i>,<i>l</i>]pyrene 11,12-Dihydrodiol 13,14-Epoxides and Deoxyadenosine
  作者：Kai-Ming Li、Mathai George、Michael L. Gross、Albrecht Seidel、Andreas Luch、Eleanor G. Rogan、Ercole L. Cavalieri

  DOI：10.1021/tx980197x

  日期：1999.9.1

  Model adducts to be used in the identification of biologically formed adducts were synthesized by reaction of fjord-region dibenzo[a,l]pyrene 11,12-dihydrodiol 13,14-epoxides (DB[a,l]PDE) and deoxyadenosine (dA). The (+/-)-anti-DB[a,l]PDE was reacted with dA in dimethylformamide at 100 degrees C for 30 min to give four DB[a, l]PDE-14-N(6)dA adducts: (-)-anti-trans (26%), (+)-anti-trans (26%), (-)-anti-cis (17%), and (+)-anti-cis (17%). The (+/-)-syn-DB[a,l]PDE was reacted with dA under the same conditions to yield four DB[a, l]PDE-14-N(6)dA adducts and one N7Ade adduct: (+)-syn-cis (19%), (+)-syn-trans (13%), (-)-syn-cis (19%), (-)-syn-trans (13%), and (+/-)-syn-DB[a,l]PDE-14-N7Ade (22%). The structures of the eight stereoisomers of DB[a,l]PDE-14-N(6)dA were unequivocally assigned by reacting optically pure (-)-anti-DB[a,l]PDE and (+)-syn-DB[a,l]PDE with dA and by a combination of NMR, circular dichroism, and fast atom bombardment mass spectrometry. Reactions at 100 degrees C yielded mainly the trans-opened adducts at the benzylic C-14 position for both (+/-)-anti-DB[a,l]PDE and (-)-anti-DB[a,l]PDE, whereas (+/-)-syn-DB[a,l]PDE and (+)-syn-DB[a,l]PDE afforded mainly cis-opened adducts. At room temperature, however, only trans-opened adducts were obtained from (+/-)-anti-DB[a,l]PDE and only cis-opened adducts from (+/-)-syn-DB[a,l]PDE. Steric hindrance created by the fjord region may be an important factor for the stereoselectivity observed at room temperature.
• Structure Elucidation of the Adducts Formed by Fjord Region Dibenzo[<i>a</i>,<i>l</i>]pyrene-11,12-dihydrodiol 13,14-Epoxides with Deoxyguanosine
  作者：Kai-Ming Li、Mathai George、Michael L. Gross、Cheng-Huang Lin、Ryszard Jankowiak、Gerald J. Small、Albrecht Seidel、Heiko Kroth、Eleanor G. Rogan、Ercole L. Cavalieri

  DOI：10.1021/tx980234k

  日期：1999.9.1

  (+/-)-anti-Dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-epoxide (+/-)-anti-DB[a,l]PDE} was reacted with deoxyguanosine (dG) in dimethylformamide at 100 degrees C for 30 min, and two sets of adducts were isolated: a mixture of (+/-)-anti-cis- & -trans-N(2)dG (43%) and a mixture of (+/-)-anti-cis- & -trans-N7Gua (45%). Both are mixtures of four stereoisomers that cannot be separated by HPLC. Similarly, (+/-)-syn-DB[a,l]PDE was reacted with dG under the same conditions, and (+/-)-syn-cis- & -trans-N(2)dG (38%) and (+/-)-syn-cis- & -trans-N7Gua (59%) were obtained. The structures of the adducts were determined by a combination of NMR and fast atom bombardment mass spectrometry. By reacting (-)-anti-DB[a,l]PDE or (+)-syn-DB[a,l]PDE with dG under the same conditions, however, optically pure N(2)dG and N7Gua isomers were obtained: (-)-anti-cis-N(2)dG (12%), (-)-anti-trans-N(2)dG (17%), (-)-anti-trans-N7Gua (43%), (+)-syn-cis-N(2)dG (7%), (+)-syn-trans-N(2)dG (3%), (+)-syn-cis-N7Gua (36%), and (+)-syn-trans-N7Gua (22%). The structures of the optically pure adducts were assigned by NMR. syn- and anti-DB[a,l]PDE-N(2)dG adducts can be distinguished by fluorescence line-narrowing spectroscopy (FLNS). Moreover, distinction between cis- and trans-stereochemistry of the adducts is also straightforward by FLNS, because the FLN spectra for the four DB[a,l]PDE-N(2)dG adducts, anti-cis, anti-trans, syn-cis, and syn-trans, are spectroscopically unique.