3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-D-ribono-1,4-lactone | 190908-03-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-D-ribono-1,4-lactone
• 英文别名: (6aR,9R,9aS)-9-hydroxy-2,2,4,4-tetra(propan-2-yl)-6,6a,9,9a-tetrahydrofuro[3,2-f][1,3,5,2,4]trioxadisilocin-8-one
• CAS: 190908-03-3
• 化学式: C₁₇H₃₄O₆Si₂
• 分子量: 390.624
• InChiKey: OZSQAHKOXXGFGK-BZUAXINKSA-N

物化性质

• 沸点：
  404.5±45.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  74.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-D-ribono-1,4-lactone 在 三乙基硅烷 、 正丁基锂 、 三氟化硼乙醚 、 silver(l) oxide 作用下， 反应 13.0h， 生成 2-amino-5-[2'-O-methyl-3',5'-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-β-D-ribofuranosyl]pyridine
  参考文献：
  名称：

  5-Substituted 2-Aminopyridine C-Nucleosides as Protonated Cytidine Equivalents:  Increasing Efficiency and Selectivity in DNA Triple-Helix Formation

  摘要：

  The easily accessible C-nucleoside 2-amino-5-(2'-deoxy-beta-D-ribofuranosyl)py (P) and its 3-methyl (P-Me) and 2'-O-methyl (P-OMe) derivatives were synthesized and incorporated as protonated cytidine equivalents in homopyrimidine oligodeoxynucleotides. T-m measurements indicate that oligonucleotides containing P or P-Me have a higher affinity to double-stranded DNA over the pH range of 6-8 than, 5-methylcytidine (C-Me) containing oligonucleotides. This increase in stability is most pronounced above pH 7.0. The average increase in T-m/modification for the dissociation of oligonucleotide d((TTTTTPTPTPTPTPT)-P-Me-P-Me-P-Me-P-Me-P-Me) from a 21-mer target duplex at pH 7.5 is 2.3 degrees C relative to oligonucleotide. d((TTTTTCTCTCTCTCT)-C-Me-C-Me-C-Me-C-Me-C-Me). The pH dependence and sequence composition effects are much less pronounced for P-Me (and also P) containing oligonucleotides than for C-Me containing ones. While oligonucleotide d((TTTCCCCTTTTCTTT)-C-Me-C-Me-C-Me-C-Me-C-Me) shows no longer any affinity to the target duplex above pH 6.5, oligonucleotide d((TTTPPPPTTTTPTTT)-P-Me-P-Me-P-Me-P-Me-P-Me) displays preserved binding with a T-m of 32.5 degrees C at pH 7.0 and even binds with a T-m of 23.3 degrees C at pH 8.0. Oligonucleotides containing P-OMe show distinctly less stable triple helices. The average decrease in T-m/modification for oligonucleotide d(TTTPTPOMeTPOMeTPOMeTPOMeTPOMeT) at pH 6.5 is 6.7 degrees C relative to the C-Me containing oligonucleotide. DNase I footprint titration experiments indicate that d((TTTTTPTPTPTPTPT)-P-Me-P-Me-P-Me-P-Me-P-Me) binds not only five times stronger to a 229 base pair DNA fragment than d((TTTTTCTCTCTCTCT)-C-Me-C-Me-C-Me-C-Me-C-Me) but also with higher selectivity; UV-melting experiments show that duplexes of d(TTTTTCTXTCTCTCT) (where X = P, P-Me, or P-OMe) With their antiparallel Watson-Crick complement are dramatically less stable (Delta T-m < -12 degrees C) at pH 8.0 than the corresponding natural duplex. Thus the new bases P and P-Me show Hoogsteen specific pairing behavior.

  DOI：

  10.1021/ja9704904
• 作为产物：
  描述：

  1,3二氯-1,1,3,3-四异丙基二硅氧烷 、 D-(+)-核糖酸-1,4-内酯 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.25h， 以51%的产率得到3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-D-ribono-1,4-lactone
  参考文献：
  名称：

  软骨素A的全合成

  摘要：

  1,2-金属盐重排加成反应作为Nozaki-Hiyama-Kishi反应的替代方法，完成了软骨素A的第一个全合成。这种转变还避免了该聚酮化合物链段的固有挑战，并提供了组装聚酮化合物骨架的新的，前所未有的策略。Z-烯酰胺的形成是通过相应酰胺与Z-乙烯基溴的Z-选择性交叉偶联来完成的。

  DOI：

  10.1002/anie.202016072

文献信息

• Towards the total synthesis of chondrochloren A: synthesis of the (<i>Z</i>)-enamide fragment
  作者：Jan Geldsetzer、Markus Kalesse

  DOI：10.3762/bjoc.16.64

  日期：——

  The stereoselective synthesis of the (Z)-enamide fragment of chondrochloren (1) is described. A Buchwald-type coupling between amide 3 and (Z)-bromide 4 was used to generate the required fragment. The employed amide 3 comprising three chiral centers was obtained through a seven-step sequence starting from ᴅ-ribonic acid-1,4-lactone. The (Z)-vinyl bromide 4 is accessible in four steps from 4-hydroxybenzaldehyde

  描述了软骨素（1）（Z）-烯酰胺片段的立体选择性合成。酰胺3和（Z）-溴化物4之间的布赫瓦尔德型偶联用于产生所需的片段。通过7个步骤从α-核糖酸-1，4-内酯开始，获得了使用的包含三个手性中心的酰胺3。（Z）-乙烯基溴化物4可从4-羟基苯甲醛分四个步骤获得。在用碘化铜（I），K2CO3和N，N'-二甲基乙烷-1,2-二胺进行广泛的实验后，两个片段之间实现了关键的交叉偶联。
• Transition State of ADP-Ribosylation of Acetyllysine Catalyzed by Archaeoglobus fulgidus Sir2 Determined by Kinetic Isotope Effects and Computational Approaches
  作者：Yana Cen、Anthony A. Sauve

  DOI：10.1021/ja910342d

  日期：2010.9.8

  Sirtuins are protein-modifying enzymes distributed throughout all forms of life. These enzymes bind NAD(+), a universal metabolite, and react it with acetyllysine residues to effect deacetylation of protein side chains. This NAD(+)-dependent deacetylation reaction has been observed for sirtuin enzymes derived from archaeal, eubacterial, yeast, metazoan, and mammalian species, suggesting conserved chemical mechanisms for these enzymes. The first chemical step of deacetylation is the reaction of NAD(+) with an acetyllysine residue which forms an enzyme-bound ADPR-peptidylimidate intermediate and nicotinamide. In this manuscript, the transition state for the ADP-ribosylation of acetyllysine is solved for an Archaeoglobus fulgidus sirtuin (Af2Sir2). Kinetic isotope effects (KIEs) were obtained by the competitive substrate method and were [1(N)-N-15] = 1.024(2), [1'(N)-C-14] = 1.014(4), [1'(N)-H-3] = 1.300(3), [2'(N)-H-3] = 1.099(5), [4'(N)-H-3] = 0.997(2), [5'(N)-H-3] = 1.020(5), [4'(N)-O-18] = 0.984(5). KIEs were calculated for candidate transition state structures using computational methods (Gaussian 03 and ISOEFF 98) in order to match computed and experimentally determined KIEs to solve the transition state. The results indicate that the enzyme stabilizes a highly dissociated oxocarbenium ionlike transition state with very low bond orders to the leaving group nicotinamide and the nucleophile acetyllysine. A concerted yet highly asynchronous substitution mechanism forms the ADPR-peptidylimidate intermediate of the sirtuin deacetylation reaction.
• 5-Substituted 2-Aminopyridine <i>C</i>-Nucleosides as Protonated Cytidine Equivalents:  Increasing Efficiency and Selectivity in DNA Triple-Helix Formation
  作者：Stefan Hildbrand、Adrian Blaser、Serge P. Parel、Christian J. Leumann

  DOI：10.1021/ja9704904

  日期：1997.6.1

  The easily accessible C-nucleoside 2-amino-5-(2'-deoxy-beta-D-ribofuranosyl)py (P) and its 3-methyl (P-Me) and 2'-O-methyl (P-OMe) derivatives were synthesized and incorporated as protonated cytidine equivalents in homopyrimidine oligodeoxynucleotides. T-m measurements indicate that oligonucleotides containing P or P-Me have a higher affinity to double-stranded DNA over the pH range of 6-8 than, 5-methylcytidine (C-Me) containing oligonucleotides. This increase in stability is most pronounced above pH 7.0. The average increase in T-m/modification for the dissociation of oligonucleotide d((TTTTTPTPTPTPTPT)-P-Me-P-Me-P-Me-P-Me-P-Me) from a 21-mer target duplex at pH 7.5 is 2.3 degrees C relative to oligonucleotide. d((TTTTTCTCTCTCTCT)-C-Me-C-Me-C-Me-C-Me-C-Me). The pH dependence and sequence composition effects are much less pronounced for P-Me (and also P) containing oligonucleotides than for C-Me containing ones. While oligonucleotide d((TTTCCCCTTTTCTTT)-C-Me-C-Me-C-Me-C-Me-C-Me) shows no longer any affinity to the target duplex above pH 6.5, oligonucleotide d((TTTPPPPTTTTPTTT)-P-Me-P-Me-P-Me-P-Me-P-Me) displays preserved binding with a T-m of 32.5 degrees C at pH 7.0 and even binds with a T-m of 23.3 degrees C at pH 8.0. Oligonucleotides containing P-OMe show distinctly less stable triple helices. The average decrease in T-m/modification for oligonucleotide d(TTTPTPOMeTPOMeTPOMeTPOMeTPOMeT) at pH 6.5 is 6.7 degrees C relative to the C-Me containing oligonucleotide. DNase I footprint titration experiments indicate that d((TTTTTPTPTPTPTPT)-P-Me-P-Me-P-Me-P-Me-P-Me) binds not only five times stronger to a 229 base pair DNA fragment than d((TTTTTCTCTCTCTCT)-C-Me-C-Me-C-Me-C-Me-C-Me) but also with higher selectivity; UV-melting experiments show that duplexes of d(TTTTTCTXTCTCTCT) (where X = P, P-Me, or P-OMe) With their antiparallel Watson-Crick complement are dramatically less stable (Delta T-m < -12 degrees C) at pH 8.0 than the corresponding natural duplex. Thus the new bases P and P-Me show Hoogsteen specific pairing behavior.
• The Total Synthesis of Chondrochloren A
  作者：Yannick Linne、Elisa Bonandi、Christopher Tabet、Jan Geldsetzer、Markus Kalesse

  DOI：10.1002/anie.202016072

  日期：2021.3.22

  The first total synthesis of chondrochloren A is accomplished using a 1,2‐metallate rearrangement addition as an alternative for the Nozaki‐Hiyama‐Kishi reaction. This transformation also avoids the inherent challenges of this polyketide segment and provides a new, unprecedented strategy to assemble polyketidal frameworks. The formation of the Z‐enamide is accomplished using a Z‐selective cross coupling

  1,2-金属盐重排加成反应作为Nozaki-Hiyama-Kishi反应的替代方法，完成了软骨素A的第一个全合成。这种转变还避免了该聚酮化合物链段的固有挑战，并提供了组装聚酮化合物骨架的新的，前所未有的策略。Z-烯酰胺的形成是通过相应酰胺与Z-乙烯基溴的Z-选择性交叉偶联来完成的。