反-菲-1,2-二醇-3,4-环氧化物 | 67737-62-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 中文名称: 反-菲-1,2-二醇-3,4-环氧化物
• 英文名称: Phenanthrene 1α,2β-diol 3β,4β-epoxide
• 英文别名: anti-1,2-trans-dihydroxy-3,4-epoxy-1,2,3,4-tetrahydrophenanthrene；1-beta,2-beta-Phenanthrenediol, 1,2,3,4-tetrahydro-3-alpha,4-alpha-epoxy-, (+-)-；(11S,12R,13R,15S)-14-oxatetracyclo[8.5.0.02,7.013,15]pentadeca-1(10),2,4,6,8-pentaene-11,12-diol
• CAS: 67737-62-6；72074-68-1
• 化学式: C₁₄H₁₂O₃
• 分子量: 228.247
• InChiKey: YMUIEZKBBVSZNE-RFQIPJPRSA-N

物化性质

• 熔点：
  164°C (dec.)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  反-菲-1,2-二醇-3,4-环氧化物 在 叠氮化锂 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以60%的产率得到(1R,2S,3R,4S)-4-Azido-1,2,3,4-tetrahydro-phenanthrene-1,2,3-triol
  参考文献：
  名称：

  Improved High-Yield Synthesis of Polycyclic Aromatic Hydrocarbon Amino Tribenzoates, Nucleophilic Components for Synthesis of Diol Epoxide-Nucleoside Adducts

  摘要：

  This report describes an improved high-yield synthesis of amino tribenzoates derived through a trans-ring opening of diol expoxides. A significant difference in the relative reactivities of benzo[a]pyrene series-1 and series-2 diol epoxide diastereomers with LiN3 has been noted. Facile triacylation of the azido triols derived through this ring-opening with benzoyl cyanide and reduction using PtO2 afforded the corresponding amines in high yields.

  DOI：

  10.1080/00397919408010618
• 作为产物：
  描述：

  1-bromo-2-naphthyl p-toluenesulfonate 在 platinum(IV) oxide sodium hydroxide 、 正丁基锂 、 三氟化硼乙醚 、 氢气 、 三溴化硼 、 乙硫醇 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醇 、 二氯甲烷 、 水 、 苯 为溶剂， 反应 14.0h， 生成 反-菲-1,2-二醇-3,4-环氧化物
  参考文献：
  名称：

  多环芳烃的二醇环氧化物和反式二羟基代谢物的新型区域和立体控制合成。致癌物质1,4-二甲基菲在湾区合成和反二醇环氧化物合成中的应用

  摘要：

  致癌的多环芳烃 (PAH) 需要代谢活化才能发挥其致瘤活性，通常是湾区概念所预测的二醇环氧化物。虽然文献中描述了许多针对这些二醇环氧化物的合成方法，但人们认为可能需要一种新的、完全不同的方法来实现这些代谢物的区域和立体化学控制的合成，尤其是湾区类似物。作者描述了 PAH 二醇环氧化物和反式二氢二醇的普遍适用、高效合成及其在假定活性代谢物的首次合成中的应用，即致癌物质 1,4-二甲基菲 (1,4-DMPh) 的湾区二醇环氧化物）。

  DOI：

  10.1021/ja00176a062

文献信息

• Synthesis and duplex-forming properties of a nonanucleotide containing an N6-deoxyadenosine adduct of a bay-region diol epoxide
  作者：Mahesh K. Lakshman、Jane M. Sayer、Haruhiko Yagi、Donald M. Jerina

  DOI：10.1021/jo00043a012

  日期：1992.8

  A protected derivative, corresponding to the adduct derived from trans opening of (+/-)-1-alpha,2-beta-dihydroxy-3-beta,4-beta-epoxy-1,2,3,4-tetrahydrophenanth rene (in which the benzylic hydroxyl and epoxide groups are trans, Phenanthrene diol epoxide-2) by the exocyclic amino group of 2-deoxyadenosine (dA), has been synthesized by couPling (+/-)-1-alpha,2-beta,3-beta-trihydroxy-4-alpha-amino-1,2,3,4-tetrahydrophenan threne with a disilyl derivative of 6-fluoro dA. The resulting pair of diastereomeric adducts was easily separated by HPLC, and the absolute configuration of each diastereomer was assigned from its CD spectrum by analogy to known tetrahydrophenanthrene analogs. The structures of these adducts were confirmed by comparison of the NMR spectra of the derived pentaacetates with those obtained for the corresponding compounds prepared from dAMP and phenanthrene diol epoxide-2. Acetylation of the free hydroxyl groups, desilylation of the sugar, 5'-O-(4,4'-dimethoxytrityl) protection, and generation of a 3'-O-[(NN-diisopropylamino)(beta-cyanoethoxy)phosphine] provided an intermediate that was incorporated, using modified solid-phase DNA synthesizer methodology, into the oligonucleotide d(GGT CA*C GAG) comprising codons 60-62 of the human K-ras b proto-oncogene sequence. The effect of an adduct on the T(m) values for duplexes formed by this nonamer with complementary strands in which the residue opposite the modified dA is T or either of the "mismatched" purine nucleosides dA or dG was determined. Replacement of T with dG opposite the modified dA has little or no effect on T(m), whereas replacement of T with dA decreases the T(m) of the modified duplex by 9-degrees-C.
• A novel regio- and stereocontrolled synthesis of diol epoxide and trans-dihydriol metabolites of polycyclic aromatic hydrocarbons. An application to the synthesis of the bay-region syn- and anti-diol epoxides of the carcinogen 1,4-dimethylphenanthrene
  作者：Masato Koreeda、Kee Yong Jung、Mitsuru Hirota

  DOI：10.1021/ja00176a062

  日期：1990.9

  stereochemically controlled synthesis of these metabolites, particularly the bay-region analogues. The authors delineate a generally applicable, efficient synthesis of PAH diol epoxides and trans-dihydrodiols and its application to the first synthesis of the putative active metabolites, the bay-region diol epoxides of the carcinogen 1,4-dimethylphenanthrene (1,4-DMPh).

  致癌的多环芳烃 (PAH) 需要代谢活化才能发挥其致瘤活性，通常是湾区概念所预测的二醇环氧化物。虽然文献中描述了许多针对这些二醇环氧化物的合成方法，但人们认为可能需要一种新的、完全不同的方法来实现这些代谢物的区域和立体化学控制的合成，尤其是湾区类似物。作者描述了 PAH 二醇环氧化物和反式二氢二醇的普遍适用、高效合成及其在假定活性代谢物的首次合成中的应用，即致癌物质 1,4-二甲基菲 (1,4-DMPh) 的湾区二醇环氧化物）。
• Improved High-Yield Synthesis of Polycyclic Aromatic Hydrocarbon Amino Tribenzoates, Nucleophilic Components for Synthesis of Diol Epoxide-Nucleoside Adducts
  作者：Mahesh K. Lakshman、Surendrakumar Chaturvedi、Roland E. Lehr

  DOI：10.1080/00397919408010618

  日期：1994.11

  This report describes an improved high-yield synthesis of amino tribenzoates derived through a trans-ring opening of diol expoxides. A significant difference in the relative reactivities of benzo[a]pyrene series-1 and series-2 diol epoxide diastereomers with LiN3 has been noted. Facile triacylation of the azido triols derived through this ring-opening with benzoyl cyanide and reduction using PtO2 afforded the corresponding amines in high yields.