2-bromo-3,5-O-di(tert-butyldimethylsilyl)-2-deoxy-D-ribono-1,4-lactone | 142329-75-7

• 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: 2-bromo-3,5-O-di(tert-butyldimethylsilyl)-2-deoxy-D-ribono-1,4-lactone
• 英文别名: 2-bromo-3,5-di-O-(tert-butyldimethysilyl)-2-deoxy-D-arabinonolactone；2-deoxy-2-bromo-3,5-di-O-(tert-butyldimethylsilyl)-γ-D-ribonolactone；2-deoxy-2-bromo-3,5-di-O-(t-butyldimethylsilyl)-D-ribono-1,4-lactone；(3R,4R,5R)-3-bromo-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-one
• CAS: 142329-75-7
• 化学式: C₁₇H₃₅BrO₄Si₂
• 分子量: 439.537
• InChiKey: KGJGQUMNPJPYJK-MGPQQGTHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.09
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-deoxy-D-ribose 在 咪唑 、 三氟甲磺酸三甲基硅酯 、 溴 、 三乙胺 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 145.5h， 生成 2-bromo-3,5-O-di(tert-butyldimethylsilyl)-2-deoxy-D-arabinono-1,4-lactone 、 2-bromo-3,5-O-di(tert-butyldimethylsilyl)-2-deoxy-D-ribono-1,4-lactone
  参考文献：
  名称：

  具有连接到核糖的C2的高半胱氨酸单元的S-核糖基同型半胱氨酸类似物的异构体类似物的合成。

  摘要：

  LuxS（S-核糖基同型半胱氨酸酶； EC 4.4.1.21）是一种催化硫醚键在S-核糖基同型半胱氨酸（SRH）催化途径中裂解的酶，产生高半胱氨酸和4,5-二羟基-2,3-戊二酮（DPD） ）。DPD是称为自动诱导剂2（AI-2）的信号分子的前体，负责负责确定为细胞与细胞之间的通讯的细菌群体感应（QS）。LuxS抑制剂应能够干扰其催化途径，从而防止自诱导分子的形成。在这项工作中，通过将相应的2-溴-2-脱氧五呋喃呋喃糖基糖与高半胱氨酸阴离子偶联来尝试合成2-脱氧-2-溴-SRH类似物。

  DOI：

  10.1016/j.bmcl.2017.03.004

文献信息

• [EN] HALOGENATED 2-DEOXY-LACTONES, 2'-DEOXY--NUCLEOSIDES, AND DERIVATIVES THEREOF<br/>[FR] 2-DÉSOXY-LACTONES HALOGÉNÉES, 2'-DÉSOXY-NUCLÉOSIDES, ET LEURS DÉRIVÉS
  申请人：UNIV CORNELL

  公开号：WO2011003018A9

  公开（公告）日：2012-11-08
• Diastereocontrolled Electrophilic Fluorinations of 2-Deoxyribonolactone: Syntheses of All Corresponding 2-Deoxy-2-fluorolactones and 2′-Deoxy-2′-fluoro-NAD⁺s
  作者：Yana Cen、Anthony A. Sauve

  DOI：10.1021/jo900637f

  日期：2009.8.21

  Methods to construct 2'-deoxy-2'-fluoro nucleosides have undergone limited improvement in the last 20 years in spite of the substantially increased value of these compounds as pharmaceuticals and as tools for studying biological processes. We herein describe a consolidated approach to synthesize precursors to these commercially and scientifically valuable compounds via diastereocontrolled fluorination of the readily available precursor 2-deoxy-D-ribonolactone. With employment of appropriate sterically bulky silyl protecting groups at the 3 and 5 positions, controlled electrophilic fluorination of the Li-ribonolactone enolate by N-fluorodibenzenesulfonamide yielded the corresponding 2-deoxy-2-fluoroarabinolactone in high isolated yield (72%) The protected 2-deoxy-2,2-difluororibonolactone was obtained similarly in high yield from a second round of electrophilic fluorination (two steps, 51% from protected ribonolactone starting material). Accomplishment of the difficult ribofluorination of the lactone was achieved by the directive effects of a diastereoselectively installed (x-trimethylsilyl group. Electrophilic fluorination of a protected 2-deoxy-2-trimethylsilylarabinolactone via enolate generation provided the protected 2-deoxy-2-fluororibolactone as the exclusive fluorinated product. The reaction also yielded the starting material, the desilylated protected 2-deoxyribonolactone, which was recycled to provide a 38% chemical yield of the fluorinated product (versus initial protected ribonolactone),after consecutive silylation and fluorination cycles. Using our fluorinated sugar precursors, we prepared the 2'-fluoroarabino-, 2'-fluororibo-, and 2',2'-difluoronicotinamide adenine dinucleotides (NAD(+)) of potential biological interest. These syntheses provide the most consolidated and efficient methods for production of sugar precursors of 2'-deoxy-2'-fluoronucleosides and have the advantage of utilizing an air-stable electrophilic fluorinating agent. The fluorinated NAD(+)s are anticipated to be useful for studying a variety of cellular metabolic and signaling processes.
• Free radical-induced C-allylation of α-bromolactones. Synthesis of 2-C-allyl-2-deoxy-d-arabino-and -d-ribono-1,4-lactones
  作者：Stephen Hanessian、Roger Léger、Marco Alpegiani

  DOI：10.1016/s0008-6215(00)90556-1

  日期：1992.4

  Application of the Keck C-allylation of organic halides to 2-bromo-2-deoxy-D-arabinonolactone resulted in the formation of mixtures of 2-C-allyl lactones. The stereochemical preferences observed were dictated by the nature of vicinal and remotely placed substituents in the lactone.
• Synthesis of isomeric analogues of S- ribosylhomocysteine analogues with homocysteine unit attached to C2 of ribose
  作者：Christiane Chbib

  DOI：10.1016/j.bmcl.2017.03.004

  日期：2017.4

  molecules. In this work, the synthesis of 2-deoxy-2-bromo-SRH analogues was attempted by the coupling of the corresponding 2-bromo-2-deoxypentafuranosyl sugars with the homocysteinate anion. The displacement of the bromide from C2 rather than the expected substitution of the mesylate group from C5 was observed leading to a novel isomeric analogue of SRH in which Hcy moiety is attached to a ribose ring via

  LuxS（S-核糖基同型半胱氨酸酶； EC 4.4.1.21）是一种催化硫醚键在S-核糖基同型半胱氨酸（SRH）催化途径中裂解的酶，产生高半胱氨酸和4,5-二羟基-2,3-戊二酮（DPD） ）。DPD是称为自动诱导剂2（AI-2）的信号分子的前体，负责负责确定为细胞与细胞之间的通讯的细菌群体感应（QS）。LuxS抑制剂应能够干扰其催化途径，从而防止自诱导分子的形成。在这项工作中，通过将相应的2-溴-2-脱氧五呋喃呋喃糖基糖与高半胱氨酸阴离子偶联来尝试合成2-脱氧-2-溴-SRH类似物。