(+/-)-cis-3-hydroxy-4-amino-1,2,3,4-tetrahydrophenanthrene | 135560-87-1

• 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: (+/-)-cis-3-hydroxy-4-amino-1,2,3,4-tetrahydrophenanthrene
• 英文别名: (3R,4S)-4-amino-1,2,3,4-tetrahydrophenanthren-3-ol
• CAS: 135560-87-1；135636-89-4；141193-99-9
• 化学式: C₁₄H₁₅NO
• 分子量: 213.279
• InChiKey: WXMUUYNEHOKKLW-TZMCWYRMSA-N

物化性质

• 沸点：
  413.8±45.0 °C(Predicted)
• 密度：
  1.219±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  46.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-cis-3-hydroxy-4-amino-1,2,3,4-tetrahydrophenanthrene 在 吡啶 、 2,6-二甲基吡啶 、 六甲基二硅氧烷 、 四丁基氟化铵 、 lithium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.25h， 生成 (3S,4R)-N⁶-(4-(3-acetoxy-1,2,3,4-tetrahydrophenanthrenyl))-5'-O-(4,4'-dimethoxytrityl)-3'-O-<(N,N-diisopropylamino)(β-cyanoethoxy)phosphinyl>-2'-deoxyadenosine
  参考文献：
  名称：

  Synthesis and site-specific incorporation of a bay-region cis ring-opened tetrahydro epoxide-deoxyadenosine adduct into a DNA oligomer

  摘要：

  Chemical synthesis of the 1,2,3,4-tetrahydrophenanthrene 3,4-epoxide adducts resulting from benzylic, cis ring-opening of the epoxide by the exocyclic amino group of 2'-deoxyadenosine (dA) is described. The approach taken consists of coupling (+/-)-cis-3-hydroxy-4-amino-1,2,3,4-tetrahydrophenanthrene with a 6-fluoro analogue of dA in which the furanose hydroxyl groups are protected. The required amino alcohol was obtained by reaction of 1,2-dihydrophenanthrene with osmium tetraoxide to form the cis 3,4-diol, conversion to the trans chlorohydrin benzoate via its orthobenzoate, displacement of the benzylic chloride by azide, hydrolysis to the cis azido alcohol, and reduction to the racemic cis amino alcohol. Coupling of the amino alcohol with the 3',5'-bis-O-(tert-butyldimethylsilyl) derivative of 6-fluoro-9-(2-deoxy-beta-D-erythro-pentofuranosyl)purine results in a pair of diastereomers that are readily separated by HPLC on silica gel. Replacement of the previously used pyridine by 2,6-lutidine significantly improved the yield for the coupling step. Both adducts were acetylated on the hydroxyl group of the hydrocarbon and then desilylated on the sugar. Absolute configurations were assigned to the adducts on the basis of the shapes of their CD spectra. The 3S,4R diastereomer (derived from the more polar, late-eluting adduct) was blocked at the 5'-sugar hydroxyl group with the 4,4'-dimethoxytrityl group and allowed to react with 2-cyanoethyl N,N-diisopropylchlorophosphoramidite to produce the desired activated nucleoside. Incorporation into the deoxynucleotide TpGpA*pGpT as the central base proceeded in good yield with minor modifications to the standard DNA synthesizer protocol.

  DOI：

  10.1021/jo00038a037
• 作为产物：
  描述：

  1,2-二氢菲 在 palladium on activated charcoal 吡啶 、 四氧化锇 、 三甲基氯硅烷 、 sodium azide 、 氢气 、 sodium methylate 、 三乙胺 、 苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 16.0h， 生成 (+/-)-cis-3-hydroxy-4-amino-1,2,3,4-tetrahydrophenanthrene
  参考文献：
  名称：

  Synthesis and site-specific incorporation of a bay-region cis ring-opened tetrahydro epoxide-deoxyadenosine adduct into a DNA oligomer

  摘要：

  Chemical synthesis of the 1,2,3,4-tetrahydrophenanthrene 3,4-epoxide adducts resulting from benzylic, cis ring-opening of the epoxide by the exocyclic amino group of 2'-deoxyadenosine (dA) is described. The approach taken consists of coupling (+/-)-cis-3-hydroxy-4-amino-1,2,3,4-tetrahydrophenanthrene with a 6-fluoro analogue of dA in which the furanose hydroxyl groups are protected. The required amino alcohol was obtained by reaction of 1,2-dihydrophenanthrene with osmium tetraoxide to form the cis 3,4-diol, conversion to the trans chlorohydrin benzoate via its orthobenzoate, displacement of the benzylic chloride by azide, hydrolysis to the cis azido alcohol, and reduction to the racemic cis amino alcohol. Coupling of the amino alcohol with the 3',5'-bis-O-(tert-butyldimethylsilyl) derivative of 6-fluoro-9-(2-deoxy-beta-D-erythro-pentofuranosyl)purine results in a pair of diastereomers that are readily separated by HPLC on silica gel. Replacement of the previously used pyridine by 2,6-lutidine significantly improved the yield for the coupling step. Both adducts were acetylated on the hydroxyl group of the hydrocarbon and then desilylated on the sugar. Absolute configurations were assigned to the adducts on the basis of the shapes of their CD spectra. The 3S,4R diastereomer (derived from the more polar, late-eluting adduct) was blocked at the 5'-sugar hydroxyl group with the 4,4'-dimethoxytrityl group and allowed to react with 2-cyanoethyl N,N-diisopropylchlorophosphoramidite to produce the desired activated nucleoside. Incorporation into the deoxynucleotide TpGpA*pGpT as the central base proceeded in good yield with minor modifications to the standard DNA synthesizer protocol.

  DOI：

  10.1021/jo00038a037

文献信息

• Three-step synthesis of chiral and sterically hindered amino alcohols based on cyclic enol phosphates
  作者：Krzysztof Owsianik、Ewa Krawczyk、Grażyna Mielniczak、Marek Koprowski、Lesław Sieroń

  DOI：10.1016/j.tet.2018.10.072

  日期：2018.12

  The new synthesis of chiral and sterically hindered 1,2-amino alcohols derivatives of 2-methyl-indane and 1,2,3,4-tethrahydrophenanthrene based on cyclic enol phosphates were investigated. The desired products were obtained using three step procedure: oxidation of accessible enol phosphates, transformation α-hydroxy ketones into corresponding oximes and finally reduction of the last one to 1,2-amino

  研究了基于环烯醇磷酸酯的2-甲基茚满和1,2,3,4-四氢菲菲的手性和空间位阻1,2-氨基醇衍生物的新合成方法。使用三个步骤的步骤即可获得所需的产物：可氧化的烯醇式磷酸酯的氧化，将α-羟基酮转化为相应的肟，最后将最后一种还原为1,2-氨基醇。找到并阐述了获得高对映选择性或非对映异构体比例的所有阶段的最佳条件。通过X射线分析证实了（3 R）-2，3-二氢-3-羟基-1 H-菲基-4-酮和相应的肟的结构和绝对构型。
• Regio and stereocontrolled synthesis of aryl cis aminoalcohols from cis glycols
  作者：Mahesh K. Lakshman、Barbara Zajc

  DOI：10.1016/0040-4039(96)00334-6

  日期：1996.4

  Reaction of aryl substituted cis diols with α-acetoxyisobutyryl chloride results in the formation of trans vicinal chlorohydrin acetates where the halide is benzylic. Displacement of chloride with azide ion, deprotection of the ester and reduction of the azide furnishes the requisite cis aminoalcohols. This facile four-step procedure results in the exclusive replacement of a benzylic hydroxyl with

  芳基取代的顺式二醇与α-乙酰氧基异丁酰氯的反应导致反式邻氯氯代乙酸酯的形成，其中卤化物是苄基的。用叠氮化物离子置换氯离子，使酯脱保护并还原叠氮化物，提供了必需的顺式氨基醇。这种简便的四步操作程序可将苄基羟基专门替换为氨基，并保留了立体化学结构。这组转化通常适用于多种顺式二醇，并且总收率非常好。