(1S,2R,3S,4R)-1-{6-Allyloxy-9-[(2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-9H-purin-2-ylamino}-1,2,3,4-tetrahydro-benzo[c]phenanthrene-2,3,4-triol | 350680-74-9

• 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: (1S,2R,3S,4R)-1-{6-Allyloxy-9-[(2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-9H-purin-2-ylamino}-1,2,3,4-tetrahydro-benzo[c]phenanthrene-2,3,4-triol
• CAS: 350680-74-9
• 化学式: C₄₃H₅₉N₅O₇Si₂
• 分子量: 814.142
• InChiKey: LIOMBGRRUSRFQM-BBYIITHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.32
• 重原子数：
  57.0
• 可旋转键数：
  11.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  153.24
• 氢给体数：
  4.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  (1S,2R,3S,4R)-1-{6-Allyloxy-9-[(2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-9H-purin-2-ylamino}-1,2,3,4-tetrahydro-benzo[c]phenanthrene-2,3,4-triol 在 吡啶 、 4-二甲氨基吡啶 、 lutidine 、 氢氟酸 、 二异丙基铵盐四氮唑 、 lithium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 [(1S,2R,3S,4R)-3,4-diacetyloxy-1-[[9-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[2-cyanoethoxy-[di(propan-2-yl)amino]phosphanyl]oxyoxolan-2-yl]-6-prop-2-enoxypurin-2-yl]amino]-1,2,3,4-tetrahydrobenzo[c]phenanthren-2-yl] acetate
  参考文献：
  名称：

  在六氟丙烷-2-醇存在下，通过脱氧鸟苷的环外N（2）-氨基对苯并[c]菲3,4-二醇1,2-环氧的顺式与反式打开的新型立体选择性控制。

  摘要：

  我们描述了八种可能的，非对映体纯，顺式和反式，R和SO（6）-烯丙基保护的N（2）-dGuo亚磷酰胺结构单元，通过顺式和反式衍生的新型有效合成方法（62-84％产率） （+/-）-3alpha，4beta-dihydroxy-1beta，2beta-epoxy-1,2,3,4-四氢苯并[c]菲[BcPh DE-1（1）]和（+/-）-3alpha的打开六氟丙烷-2-醇（HFP）介导的O（6）合成1,4beta-二羟基-1alpha，2alpha-环氧-1,2,3,4-四氢苯并[c]菲[BcPh DE-2（2）] -在环氧化合物的C-1处的-烯丙基-3′，5′-二-O-（叔丁基二甲基甲硅烷基）-2′-脱氧鸟苷（3）。只需改变反应混合物中HFP的相对用量，即可实现宽比例的顺式/反式加成产物。从而，在5当量3的存在下，DE-1（1）在HFP的5-532当量范围内观察到的顺式/反式加合物比率从17

  DOI：

  10.1021/jo020418a
• 作为产物：
  描述：

  (+/-)-3α,4β-dihydroxy-1α,2α-epoxy-1,2,3,4-tetrahydrobenzo[c]phenanthrene 、 O⁶-Allyl-3',5'-O-bis(tert-butyldimethylsilyl)-2'-deoxyguanosine 以 N,N-二甲基乙酰胺 为溶剂， 反应 5.0h， 生成 (1S,2S,3R,4S)-1-{6-Allyloxy-9-[(2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-9H-purin-2-ylamino}-1,2,3,4-tetrahydro-benzo[c]phenanthrene-2,3,4-triol 、 (1S,2R,3S,4R)-1-{6-Allyloxy-9-[(2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-9H-purin-2-ylamino}-1,2,3,4-tetrahydro-benzo[c]phenanthrene-2,3,4-triol 、 (1R,2S,3R,4S)-1-{6-Allyloxy-9-[(2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-9H-purin-2-ylamino}-1,2,3,4-tetrahydro-benzo[c]phenanthrene-2,3,4-triol 、 (1R,2R,3S,4R)-1-{6-Allyloxy-9-[(2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-9H-purin-2-ylamino}-1,2,3,4-tetrahydro-benzo[c]phenanthrene-2,3,4-triol
  参考文献：
  名称：

  O⁶-Allyl Protected Deoxyguanosine Adducts of Polycyclic Aromatic Hydrocarbons as Building Blocks for the Synthesis of Oligonucleotides

  摘要：

  We describe a synthetic strategy for the preparation of oligonucleotides using N-2-alkylated and O-6-allyl protected deoxyguanosine phosphoramidite building blocks derived from cis- and trans-opened (+/-)-7 beta ,8 alpha -dihydroxy-9 alpha, 10 alpha -epoxy-7,8,9, 10-tetrahydrobenzo[a]pyrene and (+/- )7 beta ,8 alpha -dihydroxy-9 beta, 10 beta -epoxy-7,8,9, 10-tetrahydrobenzo [a]pyrene and from trans-opened (+/-)-3 alpha ,4 beta -dihydroxy- 1 alpha ,2 alpha -epoxy-1,2,3,4-tetrahydrobenzo [c] phenanthrene. The appropriately blocked phosphoramidite building blocks were obtained as mixtures of the cis- and trans-opened diol epoxide adducts upon initial reaction of the diol epoxides with O-6-allyl-3',5'-di-O-(tert-butyldimethylsilyl)-2'-deoxyguanosine. Key to the present approach is the removal of the O-6-allyl protecting group utilizing a palladium catalyst prior to release of the constructed oligonucleotide with ammonia from the solid support. The methodology described enables a very convenient access to oligonucleotides containing cis- and trans-N-2-deoxyguanosine adducts of polycyclic aromatic hydrocarbons in different sequence contexts.

  DOI：

  10.1021/tx0002637