2'-deoxy-2'-α-C-(3-oxopropyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine | 537031-72-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 2'-deoxy-2'-α-C-(3-oxopropyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine
• 英文别名: 3-[(6aR,8R,9R,9aS)-8-(2,4-dioxopyrimidin-1-yl)-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-9-yl]propanal
• CAS: 537031-72-4
• 化学式: C₂₄H₄₂N₂O₇Si₂
• 分子量: 526.778
• InChiKey: IBUPFYJLRIMDHV-YXPKMTABSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  35
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  103
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2'-deoxy-2'-α-C-(3-oxopropyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine 在 sodium chlorite 、 potassium dihydrogenphosphate 、 2-甲基-2-丁烯 作用下， 以 叔丁醇 为溶剂， 反应 2.0h， 以72%的产率得到2'-deoxy-2'-α-C-carboxyethyl-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine
  参考文献：
  名称：

  Studies on 2′-α-C-carboxyalkyl nucleosides and their application to a stereocontrolled nucleobase exchange process

  摘要：

  对2′-α-C-羧基烷基核苷在异常的两步立体控制核苷碱基交换过程中的能力进行了研究。在硅化后，保护的2′-脱氧-2′-α-C-(羧甲基)尿苷衍生物可以通过2′-羧酸基团进行尿嘧啶基团的分子内置换，形成五碳呋喃糖γ-内酯。在相同条件下，同 homologous 2′-脱氧-2′-α-C-(羧乙基)尿苷衍生物并未产生相应的δ-内酯，而是通过尿嘧啶的消除生成相应的糖醇。五碳呋喃糖γ-内酯是通过Vorbrüggen方法进行核苷合成的良好底物，并且与任何嘧啶或嘌呤硅化核苷碱基进行完全选择性的开环反应，从而中等至高产量地生成新型的2′-C-羧甲基β-核苷。

  DOI：

  10.1039/b208786n
• 作为产物：
  描述：

  1-((2R,3R,3aS,9aR)-3-Allyl-5,5,7,7-tetraisopropyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-2-yl)-4-hydroxy-1H-pyrimidin-2-one 在 二氯乙酸 、 dimethyl sulfide borane 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 20.5h， 生成 2'-deoxy-2'-α-C-(3-oxopropyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine
  参考文献：
  名称：

  Studies on 2′-α-C-carboxyalkyl nucleosides and their application to a stereocontrolled nucleobase exchange process

  摘要：

  对2′-α-C-羧基烷基核苷在异常的两步立体控制核苷碱基交换过程中的能力进行了研究。在硅化后，保护的2′-脱氧-2′-α-C-(羧甲基)尿苷衍生物可以通过2′-羧酸基团进行尿嘧啶基团的分子内置换，形成五碳呋喃糖γ-内酯。在相同条件下，同 homologous 2′-脱氧-2′-α-C-(羧乙基)尿苷衍生物并未产生相应的δ-内酯，而是通过尿嘧啶的消除生成相应的糖醇。五碳呋喃糖γ-内酯是通过Vorbrüggen方法进行核苷合成的良好底物，并且与任何嘧啶或嘌呤硅化核苷碱基进行完全选择性的开环反应，从而中等至高产量地生成新型的2′-C-羧甲基β-核苷。

  DOI：

  10.1039/b208786n

文献信息

• Synthesis of 2‘-<i>C</i>-α-(Hydroxyalkyl) and 2‘-<i>C</i>-α-Alkylcytidine Phosphoramidites:  Analogues for Probing Solvent Interactions with RNA
  作者：Nan-Sheng Li、Joseph A. Piccirilli

  DOI：10.1021/jo062002t

  日期：2007.2.1

  Nucleoside analogues bearing 2'-C-alpha-(hydroxyalkyl) and 2'-C-alpha-alkyl substitutes have numerous applications in RNA chemistry and biology. In particular, they provide a strategy to probe the interaction between the 2'-hydroxyl group of RNA and water. To incorporate these nucleoside analogues into oligonucleotides for studies of the group II intron (Gordon, P. M.; Fong, R.; Deb, S.; Li, N.-S.; Schwans, J. P.; Ye, J.-D.; Piccirilli, J. A. Chem. Biol. 2004, 11, 237), we synthesized six new phosphoramidite derivatives of 2'-deoxy-2'-C-alpha-(hydroxyalkyl)cytidine (36: R = -(CH2)(2)OH; 38: R = -(CH2)(3)OH; 40: R = -(CH2)(4)OH) and 2'-deoxy-2'-C-alpha-alkylcytidine (37: R = -CH2CH3; 39: R = -(CH2)(2)CH3; 41: R = -(CH2)(3)CH3) from cytidine or uridine via 2'-C-alpha-allylation, followed by alkene and alcohol transformations. Phosphoramidites 36 and 37 were prepared from cytidine in overall yields of 14% (10 steps) and 7% (11 steps), respectively. Phosphoramidites 38 and 39 were prepared from uridine in overall yields of 30% (10 steps) and 13% (11 steps), respectively. Phosphoramidites 40 and 41 were synthesized from uridine in overall yields of 21% (13 steps) and 25% (14 steps), respectively.
• Studies on 2′-α-C-carboxyalkyl nucleosides and their application to a stereocontrolled nucleobase exchange process
  作者：Volker Fehring、Sally Knights、Mai-Yee Chan、Ian A. O'Neil、Richard Cosstick

  DOI：10.1039/b208786n

  日期：——

  The ability of 2′-α-C-carboxyalkyl nucleosides to undergo an unusual two-step stereocontrolled nucleobase exchange process has been investigated. Upon silylation a protected 2′-deoxy-2′-α-C-(carboxymethyl)uridine derivative can undergo intramolecular displacement of the uracil base, by the 2′-carboxylic acid group, to form a pentofuranosyl γ-lactone. Under identical conditions the homologous 2′-deoxy-2′-α-C-(carboxyethyl)uridine derivative does not yield the corresponding δ-lactone, but undergoes elimination of uracil to give the corresponding glycal. The pentofuranosyl γ-lactone is a good substrate for nucleoside synthesis by the Vorbrüggen procedures and undergoes completely stereoselective ring opening with either pyrimidine or purine silylated nucleobases to give novel 2′-C-carboxymethyl β-nucleosides in moderate to high yield.

  对2′-α-C-羧基烷基核苷在异常的两步立体控制核苷碱基交换过程中的能力进行了研究。在硅化后，保护的2′-脱氧-2′-α-C-(羧甲基)尿苷衍生物可以通过2′-羧酸基团进行尿嘧啶基团的分子内置换，形成五碳呋喃糖γ-内酯。在相同条件下，同 homologous 2′-脱氧-2′-α-C-(羧乙基)尿苷衍生物并未产生相应的δ-内酯，而是通过尿嘧啶的消除生成相应的糖醇。五碳呋喃糖γ-内酯是通过Vorbrüggen方法进行核苷合成的良好底物，并且与任何嘧啶或嘌呤硅化核苷碱基进行完全选择性的开环反应，从而中等至高产量地生成新型的2′-C-羧甲基β-核苷。