(R)-3-(tert-Butyl-dimethyl-silanyloxy)-3-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-propionaldehyde | 755037-07-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-3-(tert-Butyl-dimethyl-silanyloxy)-3-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-propionaldehyde
• CAS: 755037-07-1
• 化学式: C₁₄H₂₈O₄Si
• 分子量: 288.459
• InChiKey: NIHIHIGGYFSNBB-VXGBXAGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.12
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (R)-3-(tert-Butyl-dimethyl-silanyloxy)-3-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-propionaldehyde 在 (-)-DIP-Chloride 、 sodium hydride 、 臭氧 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Phorboxazole A viade NovoOxazole Formation 的全合成：策略和组件组装

  摘要：

  佛盒唑天然产物是癌细胞分裂最有效的抑制剂之一，但目前基本上无法从天然来源获得。已经开发了基于三组分片段偶联策略的实验室合成，以可靠的方式和前所未有的效率提供佛盒唑 A 和类似物。这是通过从两个丝氨酸衍生的酰胺依次或同时形成天然产物的两个恶唑部分来进行的，包括氧化-环化脱水。已经开发了代表碳 3-17、18-30 和 31-46 的三种预组装组件的优化制备。本文详细介绍了这三个基本构建块的设计和综合。

  DOI：

  10.1021/ja108906e
• 作为产物：
  描述：

  2-deoxy-4,5-O-isopropylidene-D-threo pentose diethyldithioacetal 在 水 、 碘 、 碳酸氢钠 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 生成 (R)-3-(tert-Butyl-dimethyl-silanyloxy)-3-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-propionaldehyde
  参考文献：
  名称：

  Phorboxazole A viade NovoOxazole Formation 的全合成：策略和组件组装

  摘要：

  佛盒唑天然产物是癌细胞分裂最有效的抑制剂之一，但目前基本上无法从天然来源获得。已经开发了基于三组分片段偶联策略的实验室合成，以可靠的方式和前所未有的效率提供佛盒唑 A 和类似物。这是通过从两个丝氨酸衍生的酰胺依次或同时形成天然产物的两个恶唑部分来进行的，包括氧化-环化脱水。已经开发了代表碳 3-17、18-30 和 31-46 的三种预组装组件的优化制备。本文详细介绍了这三个基本构建块的设计和综合。

  DOI：

  10.1021/ja108906e

文献信息

• Total Synthesis of the Reported Structure of Neaumycin B
  作者：Jiaming Ding、Amos B. Smith

  DOI：10.1021/jacs.3c06573

  日期：2023.8.23

  stereoselective total synthesis of structure 1 assigned to the macrolide natural product neaumycin B is reported in a 2.3% overall yield on 90 mg scale. The synthesis features a gram-scale nickel-catalyzed reductive cross-coupling/spiroketalization tactic to construct the spiroketal core of neaumycin B. The stereostructures of the C3–C6, C8–C14, and C20–C41 segments of synthetic neaumycin B were unambiguously

  据报道，大环内酯天然产物新霉素 B 的结构1的立体选择性全合成在 90 mg 规模上的总产率为 2.3%。该合成采用克级镍催化还原交叉偶联/螺酮化策略来构建新霉素 B 的螺酮核心。合成新霉素 B 的 C3–C6、C8–C14 和 C20–C41 片段的立体结构得到了明确验证。通过X射线晶体学。
• 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.
• 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).