{(1S,3S,4S,5R)-7,7-dimethyl-2,6,8-trioxa-4-(phenylmethoxy)-3-[(phenylmethoxy)methyl]-bicyclo[3.3.0]oct-3-yl}methan-1-ol | 153186-11-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: {(1S,3S,4S,5R)-7,7-dimethyl-2,6,8-trioxa-4-(phenylmethoxy)-3-[(phenylmethoxy)methyl]-bicyclo[3.3.0]oct-3-yl}methan-1-ol
• 英文别名: 3,6-di-O-benzyl-4-C-hydroxymethyl-1,2-O-isopropylidene-α-D-ribofuranose；3,5-di-O benzyl-4-hydroxymethyl-1,2-O-isopropylidene-β-L-ribofuranose；4-C-(Hydroxymethyl)-1,2-O-(1-methylethylidene)-3,5-bis-O-(phenylmethyl)-I(2)-L-lyxofuranose；[(3aR,5S,6S,6aR)-2,2-dimethyl-6-phenylmethoxy-5-(phenylmethoxymethyl)-6,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-5-yl]methanol
• CAS: 153186-11-9
• 化学式: C₂₃H₂₈O₆
• 分子量: 400.472
• InChiKey: NVBGHWZBQWKVNK-FBPBVXOASA-N

物化性质

• 沸点：
  518.5±50.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  29.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  66.38
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  {(1S,3S,4S,5R)-7,7-dimethyl-2,6,8-trioxa-4-(phenylmethoxy)-3-[(phenylmethoxy)methyl]-bicyclo[3.3.0]oct-3-yl}methan-1-ol 在 盐酸 、 二氯乙酸 、 正丁基锂 、 草酰氯 、 二甲基亚砜 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 0.5h， 生成 (E)-3-[(2S,3S,5R)-3-Benzyloxy-2-benzyloxymethyl-5-methoxy-4-tetradec-(Z)-ylidene-tetrahydro-furan-2-yl]-acrylic acid methyl ester
  参考文献：
  名称：

  Conformationally constrained analogues of diacylglycerol (DAG). Part 19: Asymmetric syntheses of (3R)- and (3S)-3-hydroxy-4,4-disubstituted heptono-1,4-lactones as protein kinase C (PK-C) ligands with increased hydrophilicity

  摘要：

  The stereospecific introduction of (R)- and (S)-OH groups at position C-3 of two diacylglycerol gamma-lactones (DAG-lactones) previously identified as strong protein kinase C (PK-C) ligands is presented. The compounds were designed to investigate whether the extra OH group in a specific orientation could establish an additional hydrogen bond with the C1 domain of PK-C, thus providing a DAG analogue with reduced lipophilicity. The OH groups were introduced following two different diastereoselective multistep syntheses starting from diacetone-D-glucose. The PK-C binding affinities for the new compounds were weaker in comparison to those of the parent compounds, suggesting that the extra OH does not engage efficiently in hydrogen bonding at the receptor. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00477-5
• 作为产物：
  描述：

  3-O-苄基-4-C-羟甲基-1,2-O-异亚丙基-ALPHA-D-呋喃核糖 在 正丁基锂 、 四丁基氟化铵 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 生成 {(1S,3S,4S,5R)-7,7-dimethyl-2,6,8-trioxa-4-(phenylmethoxy)-3-[(phenylmethoxy)methyl]-bicyclo[3.3.0]oct-3-yl}methan-1-ol
  参考文献：
  名称：

  Conformationally constrained analogues of diacylglycerol (DAG). Part 19: Asymmetric syntheses of (3R)- and (3S)-3-hydroxy-4,4-disubstituted heptono-1,4-lactones as protein kinase C (PK-C) ligands with increased hydrophilicity

  摘要：

  The stereospecific introduction of (R)- and (S)-OH groups at position C-3 of two diacylglycerol gamma-lactones (DAG-lactones) previously identified as strong protein kinase C (PK-C) ligands is presented. The compounds were designed to investigate whether the extra OH group in a specific orientation could establish an additional hydrogen bond with the C1 domain of PK-C, thus providing a DAG analogue with reduced lipophilicity. The OH groups were introduced following two different diastereoselective multistep syntheses starting from diacetone-D-glucose. The PK-C binding affinities for the new compounds were weaker in comparison to those of the parent compounds, suggesting that the extra OH does not engage efficiently in hydrogen bonding at the receptor. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00477-5

文献信息

• Oligonucleotides Containing Novel 4′-C- or 3′-C-(Aminoalkyl)-Branched Thymidines
  作者：Henrik M. Pfundheller、Torsten Bryld、Carl E. Olsen、Jesper Wengel

  DOI：10.1002/(sici)1522-2675(20000119)83:1<128::aid-hlca128>3.0.co;2-q

  日期：2000.1.19

  The synthesis of four novel 3′-C-branched and 4′-C-branched nucleosides and their transformation into the corresponding 3′-O-phosphoramidite building blocks for automated oligonucleotide synthesis is reported. The 4′-C-branched key intermediate 11 was synthesized by a convergent strategy and converted to its 2′-O-methyl and 2′-deoxy-2′-fluoro derivatives, leading to the preparation of novel oligonucleotide

  报道了四种新型 3'-C-支链和 4'-C-支链核苷的合成及其转化为相应的 3'-O-亚磷酰胺结构单元以用于自动寡核苷酸合成。4'-C-支化关键中间体11通过收敛策略合成并转化为其2'-O-甲基和2'-脱氧-2'-氟衍生物，从而制备出含有4'-的新型寡核苷酸类似物C-(氨基甲基)-2'-O-甲基单体X和4'-C-(氨基甲基)-2'-脱氧-2'-氟单体Y(方案2和3)。一般来说，与未修饰的参考相比，这些类似物对互补单链 DNA 和 RNA 的结合亲和力增加（表 1）。2'-O-甲基-RNA寡核苷酸中单体X或单体Y的存在对2'-O-甲基-RNA寡核苷酸对DNA和RNA的结合亲和力具有负面影响。从 3'-C-烯丙基衍生物 28 开始，合成了 3'-C-(3-氨基丙基)-保护的核苷和 3'-O-亚磷酰胺衍生物，从而产生了含有 3'-C-(3-氨基丙基）胸苷单体Z或相应的3'-C-（3-氨基丙基）-2'-O
• Synthesis of 4′-<i>C</i>-Methylnucleosides
  作者：Toshiaki Waga、Tomoko Nishizaki、Isao Miyakawa、Hiroshi Ohrui、Hiroshi Meguro

  DOI：10.1271/bbb.57.1433

  日期：1993.1

  Several 4′-C-methylnucleosides were prepared. 1H-NMR studies on these nucleosides showed that they have the 3′-exo furanose ring conformation different from the 3′-endo conformation of natural nucleosides.

  制备了几种 4′-C-甲基核苷。对这些核苷的 1H-NMR 研究表明，它们具有不同于天然核苷 3′-内向构象的 3′-外向呋喃糖环构象。
• Free-Radical Ring Closure to Conformationally Locked α-<scp>l</scp>-Carba-LNAs and Synthesis of Their Oligos: Nuclease Stability, Target RNA Specificity, and Elicitation of RNase H
  作者：Qing Li、Fengfeng Yuan、Chuanzheng Zhou、Oleksandr Plashkevych、Jyoti Chattopadhyaya

  DOI：10.1021/jo100900v

  日期：2010.9.17

  A new class of conformationally constrained nucleosides, α-l-ribo-carbocyclic LNA thymidine (α-l-carba-LNA-T, LNA is an abbreviation of locked nucleic acid) analogues and a novel “double-locked” α-l-ribo-configured tetracyclic thymidine (6,7′-methylene-bridged-α-l-carba-LNA-T) in which both the sugar puckering and glycosidic torsion are simultaneously constrained, have been synthesized through a key

  一类新的构象受限的核苷，α-的升-核糖-碳环LNA胸苷（α-升-carba-LNA-T，LNA是锁核酸的缩写）类似物和一种新颖的“双锁定”α-升-核糖结构的四环胸苷（6,7'-亚甲基-桥联的-α- 1-碳-LNA-T），其中糖的起皱和糖苷的扭曲同时受到限制，这是通过涉及5- exo游离的关键步骤合成的-自由基分子内环化。这些α- l-carba-LNA类似物随后已转化为相应的亚磷酰胺，并掺入了等序反义寡核苷酸（AONs）中，然后对它们的双链体进行了热变性，核酸酶稳定性和RNase H募集能力进行了研究。与天然异源双链体相比，在AON / RNA异源双链体的AON链中引入单个6'，7'-取代的α- 1 -carba-LNA-T修饰导致T m降低2-3°C，而已发现在AON链中相同位置的亲本2'-oxa-α- 1 -LNA-T修饰导致T m增加3-5°C。这表明6'和7'取代导致修饰的异源双链体的热稳定性大大降低，尤其是位于α