(3S)-3-[tert-butyl(dimethyl)silyl]oxy-3-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]propanal | 83685-87-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S)-3-[tert-butyl(dimethyl)silyl]oxy-3-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]propanal
• CAS: 83685-87-4
• 化学式: C₁₄H₂₈O₄Si
• 分子量: 288.459
• InChiKey: NIHIHIGGYFSNBB-NWDGAFQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.12
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3S)-3-[tert-butyl(dimethyl)silyl]oxy-3-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]propanal 在 正丁基锂 、 氨 、 二异丙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 30.83h， 生成
  参考文献：
  名称：

  Chemical synthesis and characterization of duplex DNA containing a new base pair: a nondisruptive, benzofused pyrimidine analog

  摘要：

  A new base pair appropriate for incorporation into B-DNA was designed with the goal of allowing fusion of a benzene substituent across the 4 and 5 carbons of a pyrimidine analog. Such a residue may have utility in the preparation of DNA duplexes bearing precisely spatially positioned and conformationally constrained unnatural substituents such as reporter groups. The design called for the incorporation of the beta-anomer of a C-linked deoxyriboside of 2-hydroxyquinoline (dQ) opposite the beta-N9 deoxyriboside of 2-aminopurine (dAP). Several duplex DNAs were synthesized containing this new base pair as well as the analog in which 2-hydroxypyridine replaces 2-hydroxyquinoline (dP). Phosphoramidites 17 and 18 were synthesized and incorporated into synthetic oligonucleotides using automated methodology. That dQ and dP had been incorporated without chemical modification was proven by enzymatic digestion of the synthetic oligonucleotides to the component nucleosides and analysis by HPLC. Native polyacrylamide gel electrophoresis revealed that admixture of complementary strands containing dP or dQ opposite dAP gave new substances with mobility comparable to a duplex DNA of the same length containing only Watson-Crick base pairs. Solution circular dichroism measurements were consistent with these substances existing in the B conformation. T(m), DELTAH, and DELTAS were measured for synthetic duplex DNAs containing pairings of dQ and dP with dAP, dA, dC, dG, and dT. Of these, duplexes in which dAP was the partner of dP or dQ were most thermodynamically stable (DELTAG 25-degrees-C) and highest melting, with T(m) values lower by 1 to 5-degrees-C than the corresponding dA.dT-containing duplex. Solution H-1 NMR measurements from delta 11-15 on an 11-mer duplex containing the dAP.dQ pair were diagnostic for the presence of 11 base pairs. The resonance for the dAP-dQ base pair was assigned on the basis of a combination of 1D NOE measurements, temperature-dependent line width, and chemical shift measurements. We conclude that dP and dQ are competent base-pairing partners for dAP in duplex DNA and are reasonable condidates for use in the design of novel base-pairing nucleoside analogs.

  DOI：

  10.1021/jo00060a045
• 作为产物：
  描述：

  2-deoxy-D-ribose 在 咪唑 、 对甲苯磺酸 、 臭氧 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 35.0h， 生成 (3S)-3-[tert-butyl(dimethyl)silyl]oxy-3-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]propanal
  参考文献：
  名称：

  天然6-氯四氢呋喃产乙酸原素的两种可能的非对映异构体的全合成及其立体结构阐明

  摘要：

  天然6-氯四氢呋喃产乙酸原1的两种可能的非对映异构体的首次全合成已经完成。合成路线设有-5-外- TET环合，ž选择性Wittig反应和Julia烯为共轭二烯和烯炔部分和立体选择性氯化的结构。通过比较其1 H和13 C NMR数据以及比旋光度与天然产物的比旋光度，可以阐明天然（-）-6-氯四氢呋喃产乙酸原蛋白1的绝对构型。

  DOI：

  10.1002/chem.201703234

文献信息

• Efforts toward the Expansion of the Genetic Alphabet:  Information Storage and Replication with Unnatural Hydrophobic Base Pairs
  作者：Anthony K. Ogawa、Yiqin Wu、Dustin L. McMinn、Jianquan Liu、Peter G. Schultz、Floyd E. Romesberg

  DOI：10.1021/ja9940064

  日期：2000.4.1

  whose pairing in duplex DNA is based on interbase hydrophobic interactions. We show that the stability and selectivity of such unnatural base pairs may be comparable to, or even exceed, that of native pairs. We also demonstrate that several unnatural base pairs are incorporated into DNA by Klenow fragment of Escherichia coli DNA polymerase I with an efficiency equivalent to that of native DNA synthesis

  对互补核碱基之间的链间氢键的忠实识别构成了遗传密码的基础。复制包含稳定第三个碱基对的 DNA 的能力将允许通过用第三个补充遗传字母表的现有两个碱基对来扩展 DNA 的信息内容。我们报告了非天然核碱基的优化，其在双链 DNA 中的配对基于碱基间疏水相互作用。我们表明，这种非天然碱基对的稳定性和选择性可能与天然碱基对相当，甚至超过。我们还证明了几个非天然碱基对通过大肠杆菌 DNA 聚合酶 I 的 Klenow 片段掺入 DNA，其效率与天然 DNA 合成的效率相当。而且，
• A new synthetic approach for 4(S)-hydroxycyclopent-2-enone: a precursor to prostanoid synthesis
  作者：Chih-Tsung Chang、Sheila H. Jacobo、William S. Powell、John A. Lawson、Garret A. FitzGerald、Domenico Pratico、Joshua Rokach

  DOI：10.1016/j.tetlet.2005.07.035

  日期：2005.9

  A new and efficient approach to 4(S)-hydroxycyclopent-2-enone is presented. This methodology allows the preparation of 4(S)-hydroxycyclopent-2-enone in large scale and with high optical purity.

  提出了一种新的高效的4（S）-羟基环戊-2-烯酮的方法。该方法允许大规模且具有高光学纯度的制备4（S）-羟基环戊-2-烯酮。
• Stereocontrolled syntheses of C-linked deoxyribosides of 2-hydroxypyridine and 2-hydroxyquinoline
  作者：Marjorie S. Solomon、Paul B. Hopkins

  DOI：10.1016/s0040-4039(00)92690-x

  日期：1991.7

  2'-Deoxy-C-ribosides 4 and 5 were prepared in optically active form by a route expected to be generally useful for the synthesis of the alpha- or beta-anomers of 2'-deoxy-C-ribosides. Key steps are the addition of an organometallic reagent to aldehyde 7, mesylation of the resulting alcohol, and stereospecific deprotection/cyclization to yield the 2'-deoxy-C-riboside (7 + 8 --> 9/10; 9 --> 11).
• Chemical synthesis and characterization of duplex DNA containing a new base pair: a nondisruptive, benzofused pyrimidine analog
  作者：Marjorie S. Solomon、Paul B. Hopkins

  DOI：10.1021/jo00060a045

  日期：1993.4

  A new base pair appropriate for incorporation into B-DNA was designed with the goal of allowing fusion of a benzene substituent across the 4 and 5 carbons of a pyrimidine analog. Such a residue may have utility in the preparation of DNA duplexes bearing precisely spatially positioned and conformationally constrained unnatural substituents such as reporter groups. The design called for the incorporation of the beta-anomer of a C-linked deoxyriboside of 2-hydroxyquinoline (dQ) opposite the beta-N9 deoxyriboside of 2-aminopurine (dAP). Several duplex DNAs were synthesized containing this new base pair as well as the analog in which 2-hydroxypyridine replaces 2-hydroxyquinoline (dP). Phosphoramidites 17 and 18 were synthesized and incorporated into synthetic oligonucleotides using automated methodology. That dQ and dP had been incorporated without chemical modification was proven by enzymatic digestion of the synthetic oligonucleotides to the component nucleosides and analysis by HPLC. Native polyacrylamide gel electrophoresis revealed that admixture of complementary strands containing dP or dQ opposite dAP gave new substances with mobility comparable to a duplex DNA of the same length containing only Watson-Crick base pairs. Solution circular dichroism measurements were consistent with these substances existing in the B conformation. T(m), DELTAH, and DELTAS were measured for synthetic duplex DNAs containing pairings of dQ and dP with dAP, dA, dC, dG, and dT. Of these, duplexes in which dAP was the partner of dP or dQ were most thermodynamically stable (DELTAG 25-degrees-C) and highest melting, with T(m) values lower by 1 to 5-degrees-C than the corresponding dA.dT-containing duplex. Solution H-1 NMR measurements from delta 11-15 on an 11-mer duplex containing the dAP.dQ pair were diagnostic for the presence of 11 base pairs. The resonance for the dAP-dQ base pair was assigned on the basis of a combination of 1D NOE measurements, temperature-dependent line width, and chemical shift measurements. We conclude that dP and dQ are competent base-pairing partners for dAP in duplex DNA and are reasonable condidates for use in the design of novel base-pairing nucleoside analogs.
• Total Synthesis of Two Possible Diastereomers of Natural 6-Chlorotetrahydrofuran Acetogenin and Its Stereostructural Elucidation
  作者：Hiroyoshi Takamura、Tomoya Katsube、Kazuki Okamoto、Isao Kadota

  DOI：10.1002/chem.201703234

  日期：2017.12.6

  The first total synthesis of two possible diastereomers of natural 6‐chlorotetrahydrofuran acetogenin 1 has been achieved. The synthetic route features 5‐exo‐tet cyclization, Z selective Wittig reaction and Julia olefination for the construction of conjugated diene and enyne moieties, and stereoselective chlorination. Comparison of their 1H and 13C NMR data and specific rotation with those of the natural

  天然6-氯四氢呋喃产乙酸原1的两种可能的非对映异构体的首次全合成已经完成。合成路线设有-5-外- TET环合，ž选择性Wittig反应和Julia烯为共轭二烯和烯炔部分和立体选择性氯化的结构。通过比较其1 H和13 C NMR数据以及比旋光度与天然产物的比旋光度，可以阐明天然（-）-6-氯四氢呋喃产乙酸原蛋白1的绝对构型。