(R)-3-((tert-butyldiphenylsilyl)oxy)propane-1,2-diol | 125111-27-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (R)-3-((tert-butyldiphenylsilyl)oxy)propane-1,2-diol
• 英文别名: (R)-3-(t-butyldiphenylsilyloxy)propane-1,2-diol；1,2-Propanediol, 3-[[(1,1-dimethylethyl)diphenylsilyl]oxy]-, (2R)-；(2R)-3-[tert-butyl(diphenyl)silyl]oxypropane-1,2-diol
• CAS: 125111-27-5
• 化学式: C₁₉H₂₆O₃Si
• 分子量: 330.499
• InChiKey: RYZYNNLPABISLU-MRXNPFEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.92
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-3-((tert-butyldiphenylsilyl)oxy)propane-1,2-diol 在 吡啶 、 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 21.0h， 生成 2,2-Dimethyl-propionic acid (R)-3-(tert-butyl-diphenyl-silanyloxy)-2-(toluene-4-sulfonyloxy)-propyl ester
  参考文献：
  名称：

  Glycidol-carbohydrate hybrids: a new family of DNA alkylating agents

  摘要：

  Novel and chiral glycidol-carbohydrate hybrids possessing an epoxy group as a DNA alkylating moiety were designed and synthesized. These artificial hybrids selectively alkylated DNA at the N-7 sites of the guanines and cleaved DNA without any additives. The binding ability of the glycidol was significantly enhanced by the attachment of the carbohydrate. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0960-894x(03)00659-0
• 作为产物：
  描述：

  2-((叔丁基二苯基甲硅烷基)氧基)乙酸甲酯 在 锂硼氢 、 sodium acetate 、 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 (R)-3-((tert-butyldiphenylsilyl)oxy)propane-1,2-diol
  参考文献：
  名称：

  来自碳酸钡的高对映体纯（叔丁基二苯基甲硅烷氧基甲基）环氧乙烷

  摘要：

  摘要 开发了以碳酸钡为原料合成(2R)-(叔丁基二苯基甲硅烷氧基甲基)环氧乙烷和(2S)-对映异构体的方法。制备乙醇酸甲酯或异羟肟酸酯类似物，然后与 (S)-(-)-甲基对甲苯基亚砜或 (R)-对映异构体反应以制备 β-酮亚砜。从亚砜中，我们在高度选择性的亚砜基团导向的氢化物还原中制备了非对映异构醇，然后进行普默勒重排反应，然后脱保护产生对映体二醇。(2R)-(叔丁基二苯基甲硅烷氧基甲基)环氧乙烷和它的(2S)-对映异构体以56%的总产率从碳酸钡衍生自这些二醇。开发此方法是为了方便获取这些化合物的同位素标记类似物。

  DOI：

  10.1080/00397919808004924

文献信息

• Scope and Mechanism of the Pt-Catalyzed Enantioselective Diboration of Monosubstituted Alkenes
  作者：John R. Coombs、Fredrik Haeffner、Laura T. Kliman、James P. Morken

  DOI：10.1021/ja4041016

  日期：2013.7.31

  The Pt-catalyzed enantioselective diboration of terminal alkenes can be accomplished in an enantioselective fashion in the presence of chiral phosphonite ligands. Optimal procedures and the substrate scope of this transformation are fully investigated. Reaction progress kinetic analysis and kinetic isotope effects suggest that the stereodefining step in the catalytic cycle is olefin migratory insertion

  Pt 催化的末端烯烃的对映选择性二硼化可以在手性亚膦酸酯配体存在下以对映选择性方式完成。对这种转化的最佳程序和底物范围进行了充分研究。反应进程动力学分析和动力学同位素效应表明催化循环中的立体定义步骤是烯烃迁移插入 Pt-B 键。密度泛函理论分析与其他实验数据相结合，表明插入反应将铂定位在基板的内部碳上。该反应的立体化学模型得到了改进，该模型既符合这些特征又符合 Pt-配体复合物的晶体结构。
• Pt-Catalyzed Enantioselective Diboration of Terminal Alkenes with B₂(pin)₂
  作者：Laura T. Kliman、Scott N. Mlynarski、James P. Morken

  DOI：10.1021/ja9047762

  日期：2009.9.23

  The Pt-catalyzed enantioselective addition of bis(pinacolato)diboron to simple monosubstituted alkenes is described. This reaction occurs in the presence of a readily available chiral phosphonite ligand and is effective with a variety of terminal alkene substrates. Importantly, the reaction can operate with catalyst loadings of only 1 mol % Pt. While oxidation of the intermediate 1,2-bis(boronate)

  描述了 Pt 催化的双（频哪醇）二硼对简单单取代烯烃的对映选择性加成。该反应在容易获得的手性亚膦酸酯配体存在下发生，并且对多种末端烯烃底物有效。重要的是，该反应可以在催化剂负载仅为 1 mol% Pt 的情况下进行。虽然中间体 1,2-双(硼酸酯)酯的氧化提供手性 1,2-二醇作为反应产物，但中间体也可进行同系化/氧化以提供手性 1,4-二醇作为反应产物.
• Base-Pairing Properties of a Structural Isomer of Glycerol Nucleic Acid
  作者：Phaneendrasai Karri、Venkateshwarlu Punna、Keunsoo Kim、Ramanarayanan Krishnamurthy

  DOI：10.1002/anie.201300795

  日期：2013.5.27

  limit! IsoGNA (a structural isomer of GNA) was found—in sharp contrast to GNA—to be highly restricted in its ability to base‐pair with itself and other nucleic acids. While homogeneous sequences (e.g. isoGNA(A)16) formed duplexes, the heterogeneous sequences showed no base‐pairing. This exemplifies the limitations of canonical nucleobases as the recognition elements in simpler, more primitive phosphate

  知道你的极限！与GNA形成鲜明对比的是，发现IsoGNA（GNA的结构异构体）在与自身和其他核酸碱基配对的能力上受到严格限制。虽然同质序列（例如isoGNA（A）16）形成双链体，但异质序列未显示碱基配对。这举例说明了在更简单，更原始的磷酸盐骨架中作为识别元件的规范核碱基的局限性。
• Synthesis of phosphoramidites of isoGNA, an isomer of glycerol nucleic acid
  作者：Keunsoo Kim、Venkateshwarlu Punna、Phaneendrasai Karri、Ramanarayanan Krishnamurthy

  DOI：10.3762/bjoc.10.220

  日期：——

  IsoGNA, an isomer of glycerol nucleic acid GNA, is a flexible (acyclic) nucleic acid with bases directly attached to its linear backbone. IsoGNA exhibits (limited) base-pairing properties which are unique compared to other known flexible nucleic acids. Herein, we report on the details of the preparation of isoGNA phosphoramidites and an alternative route for the synthesis of the adenine derivative. The synthetic improvements described here enable an easy access to isoGNA and allows for the further exploration of this structural unit in oligonucleotide chemistry thereby spurring investigations of its usefulness and applicability.

  IsoGNA，甘油核酸GNA的异构体，是一种灵活（非环状）的核酸，其碱基直接连接到其线性骨架上。与其他已知的灵活核酸相比，IsoGNA表现出（有限的）碱基配对特性。在这里，我们报告了IsoGNA磷酰胺酯的制备细节以及腺嘌呤衍生物合成的另一种途径。这里描述的合成改进使得易于获得IsoGNA，并允许进一步探索这种结构单元在寡核苷酸化学中的应用，从而推动对其有用性和适用性的研究。
• Synthesis of L-Dioxolane Nucleosides and Related Chemistry
  作者：Chengyi Liang、Doo Won Lee、M. Gary Newton、Chung K. Chu

  DOI：10.1021/jo00111a012

  日期：1995.3

  (+)-L- or (+)-(2R,4S)-1-[4-(hydroxymethyl)-1,3-dioxolan-2-yl]-5-fluorouracil (25) and other novel classes of 1,3-dioxolane nucleosides have been synthesized. Coupling of 2-methoxy-4-[[(tert-butyldiphenylsilyl)oxy]methyl]-1,3-dioxolane (23) or 2-methyl-1,3-dioxolane (9) with silylated g-fluorouracil, thymine, cytosine, and 5-chlorocytosine in the presence of TMSOTf gave the corresponding 1,3-dioxolane nucleosides. These nucleosides were decomposed and rearranged to the ring-opened products in certain reaction conditions. It was found that 5-fluorouricil nucleosides (12 and 25) were relatively more stable than the thymine or cytosine derivatives (10, 13, and 16). Bulky protecting group (TBDPS) at the 1,3-dioxolane moiety in compound 24 may also contribute the stability to the 1,3-dioxolane nucleosides. The structures of these novel 1,3-dioxolane nucleosides and ring-opened products have been assigned by NMR spectra, and the mechanisms of decomposition and rearrangement to the ring opened products were discussed.

  (+)-L-或(+)-(2R,4S)-1-[4-(羟甲基)-1,3-二氧戊环-2-基]-5-氟尿嘧啶（25）和其他新型1,3-二氧戊环核苷已被合成。2-甲氧基-4-[[(叔丁基二苯基硅基)氧基]甲基]-1,3-二氧戊环（23）或2-甲基-1,3-二氧戊环（9）与硅化的α-氟尿嘧啶、胸腺嘧啶、胞嘧啶和5-氯胞嘧啶在TMSOTf的存在下偶联，得到相应的1,3-二氧戊环核苷。这些核苷在某些反应条件下分解并重排为开环产物。发现5-氟尿嘧啶核苷（12和25）比胸腺嘧啶或胞嘧啶衍生物（10、13和16）相对更稳定。化合物24中1,3-二氧戊环部分的庞大保护基团（TBDPS）也可能为1,3-二氧戊环核苷的稳定性做出贡献。这些新型1,3-二氧戊环核苷和开环产物的结构已通过NMR光谱确定，并讨论了分解和重排到开环产物的机制。