(3aR,5R,6S,6aR)-5-<2-(tert-butyldimethylsiloxy)ethyl>-tetrahydro-2,2-dimethylfuro<2,3-d>-1,3-dioxol-6-ol | 189165-94-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aR,5R,6S,6aR)-5-<2-(tert-butyldimethylsiloxy)ethyl>-tetrahydro-2,2-dimethylfuro<2,3-d>-1,3-dioxol-6-ol
• 英文别名: 6-O-(tert-butyldimethylsilyl)-5-deoxy-1,2-O-isopropylidene-α-D-xylo-hexofuranose；6-O-[Tert-butyl(dimethyl)silyl]-5-deoxy-1,2-O-(1-methylethylidene)-alpha-D-xylo-hexofuranose；(3aR,5R,6S,6aR)-5-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-ol
• CAS: 189165-94-4
• 化学式: C₁₅H₃₀O₅Si
• 分子量: 318.486
• InChiKey: CLBRXTGYUZGJAJ-YVECIDJPSA-N

物化性质

• 沸点：
  362.5±37.0 °C(predicted)
• 密度：
  1.026±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.64
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3aR,5R,6S,6aR)-5-<2-(tert-butyldimethylsiloxy)ethyl>-tetrahydro-2,2-dimethylfuro<2,3-d>-1,3-dioxol-6-ol 在 chromium(VI) oxide 、 sodium tetrahydroborate 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 吡啶 、 乙醇 、 乙酸酐 为溶剂， 生成 5-deoxy-1,2-O-isopropylidene-α-D-ribo-hexofuranose
  参考文献：
  名称：

  从核苷 C3' 自由基的 C2' 中消除氯（自由基）或甲苯磺酸盐（阴离子）作为假设发生在核糖核苷酸还原酶活性位点的模型反应1

  摘要：

  2'-氯-2'-脱氧核苷 5'二磷酸的 H3' 离子生成 C3' 自由基被提议 2a,c 引发反应，导致 RDPR 失活。6 氯化物的自发损失和 OH3 ' 质子向谷氨酸的转移将产生 2'-脱氧-3'-酮核苷酸中间体，而不涉及 R1 上的半胱氨酸对。2a,c 连续消除（H2'/碱基和 H4'/焦磷酸盐）会产生迈克尔受体 2-亚甲基-3(2 H)-呋喃酮，这会影响酶的共价失活。7 我们最近展示了一种可能产生迈克尔受体的机制替代方案，该替代方案涉及从模型 2' 取代核苷的 C2' 中丢失一个自由基，而不是一个阴离子物质。8,9 因此，处理 2'-（叠氮、溴、氯、碘、或甲硫基）核苷 3 '-硫代碳酸酯与三丁基锡烷/AIBN 导致 2 ' 取代基丢失，作为假定的自由基，在生成 C3 ' 自由基后得到 2 ',3'-二脱氢-2',3' 双脱氧衍生物（没有O3'); 而具有 2 '-氟或 2'-O-（甲磺酰基或甲苯磺酰基）取代基的

  DOI：

  10.1021/ja970171c
• 作为产物：
  描述：

  1,2-o-异亚丙基-alpha-d-呋喃葡萄糖-3-乙酸酯 在 咪唑 、 sodium hydroxide 、 硼烷四氢呋喃络合物 、 2-甲基-2-丁烯 、 双氧水 、 碘 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 5.5h， 生成 (3aR,5R,6S,6aR)-5-<2-(tert-butyldimethylsiloxy)ethyl>-tetrahydro-2,2-dimethylfuro<2,3-d>-1,3-dioxol-6-ol
  参考文献：
  名称：

  Reversible Charge-Accelerated Oxy-Cope Rearrangements

  摘要：

  An asymmetric synthesis of the oxetane-containing norbornanone 23 and its coupling to trans-1-propenyllithium to give 24 are reported, in tandem with the preparation of the related alcohols 28 and 30. All three divinyl carbinols undergo anionic oxy-Cope rearrangement very rapidly at low temperature. Quenching of 24(-)K(+) and 28(-)K(+) under these conditions with water or various aqueous salt solutions results in protonation of the alkoxides. If these reaction mixtures are poured instead onto cold (0 degrees C) silica gel, their sigmatropically related ketones are isolated in very good yield. Whereas the 24(-)K(+) <--(-->) 25(-)K(+) equilibrium pair is not reactive to molecular oxygen, 30(-)K(+) is directly converted into an a-hydroperoxy ketone under comparable conditions. These and additional observations are rationalized in the context of atropisomerism involving conversion of oxygen-up enolates, formed reversibly under kinetically controlled conditions, into their thermodynamically favored, more reactive oxygen-down conformers.

  DOI：

  10.1021/jo982002w

文献信息

• Biomimetic modeling of the abstraction of H3′ by ribonucleotide reductases. 1,5-Hydrogen atom transfer of H3 to aminyl and oxyl, but not thiyl, free radicals in homoribofuranose derivatives
  作者：Zhiqiang Guo、Mirna C Samano、Jan W Krzykawski、Stanislaw F Wnuk、Gregory J Ewing、Morris J Robins

  DOI：10.1016/s0040-4020(99)00238-0

  日期：1999.4

  resulted in abstraction of H3 by a [1,5]-hydrogen atom shift. Transfer of 2H from the stannane to •C3 effected incorporation of deuterium at C3. Analogous treatment of 6-azido-6-deoxy-D-ribo-hexofuranose derivatives gave C3-deuterated aminosugars. In contrast, no deuterium incorporation was detected upon parallel treatment of 6-thio-D-ribo-hexofuranose derivatives. Abstraction of H3′ by a thiyl radical

  用Bu 3 SnD / AIBN /苯/Δ从高纯呋喃核糖（5-脱氧-D-核糖-六呋喃糖）6- O-硝基酯生成6-氧自由基导致H3被[1,5]-氢原子夺取转移。的转移2从锡烷向•C3 H在C3实现氘的掺入。对6-叠氮基-6-脱氧-D-核糖-六呋喃糖衍生物的类似处理得到C3-氘代的氨基糖。相反，在平行处理6-硫代-D-核糖时未检测到氘掺入-六呋喃糖衍生物。巯基（•SCys）提取H3'是假定的第一步，反应是核糖核苷酸还原酶用于将核糖核苷酸转化为2'-脱氧核苷酸的反应。讨论了有关酶反应级联反应的结果，该级联反应将H3'的提取与C2'中不可逆的水损失耦合在一起。
• 10.1002/1099-0690(200006)2000:12<2187::aid-ejoc2187<3.0.co;2-2
  作者：Paquette, Leo、Zeng, Qingbei、Wang, Hui-Ling、Shih, Tzenge-Lien

  DOI：10.1002/1099-0690(200006)2000:12<2187::aid-ejoc2187<3.0.co;2-2

  日期：——
• Synthesis of stereodefined Z-vinyl iodides from carbohydrates as a prelude to C/D ring assembly in taxanes
  作者：Leo A. Paquette、Tzenge-Lien Shih、Qingbei Zeng、John E. Hofferberth

  DOI：10.1016/s0040-4039(99)00546-8

  日期：1999.4

  D-Mannitol has been transformed into 10 and 14, while D-glucose has served as precursor to 20. In the latter example, key steps include stereocontrolled vinylation, oxidative fragmentation of the tetrahydrofuran-2,3-diol, oxetane ring closure, and highly stereoselective iodoolefination. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Reversible Charge-Accelerated Oxy-Cope Rearrangements
  作者：Hon-Chung Tsui、Leo A. Paquette

  DOI：10.1021/jo982002w

  日期：1998.12.1

  An asymmetric synthesis of the oxetane-containing norbornanone 23 and its coupling to trans-1-propenyllithium to give 24 are reported, in tandem with the preparation of the related alcohols 28 and 30. All three divinyl carbinols undergo anionic oxy-Cope rearrangement very rapidly at low temperature. Quenching of 24(-)K(+) and 28(-)K(+) under these conditions with water or various aqueous salt solutions results in protonation of the alkoxides. If these reaction mixtures are poured instead onto cold (0 degrees C) silica gel, their sigmatropically related ketones are isolated in very good yield. Whereas the 24(-)K(+) <--(-->) 25(-)K(+) equilibrium pair is not reactive to molecular oxygen, 30(-)K(+) is directly converted into an a-hydroperoxy ketone under comparable conditions. These and additional observations are rationalized in the context of atropisomerism involving conversion of oxygen-up enolates, formed reversibly under kinetically controlled conditions, into their thermodynamically favored, more reactive oxygen-down conformers.
• Elimination of Chlorine (Radical) or Tosylate (Anion) from C2‘ of Nucleoside C3‘ Free Radicals as Model Reactions Postulated To Occur at the Active Site of Ribonucleotide Reductases¹
  作者：Morris J. Robins、Zhiqiang Guo、Stanislaw F. Wnuk

  DOI：10.1021/ja970171c

  日期：1997.4.1

  involved loss of a radical, rather than an anionic, species from C2 ′ of model 2′-substituted nucleosides. 8,9 Thus, treatment of 2 ′-(azido, bromo, chloro, iodo, or methylthio)nucleoside 3 ′-thionocarbonates with tributylstannane/AIBN resulted in loss of the 2 ′substituents, as presumed radicals, to give 2 ′,3′-didehydro-2′,3′dideoxy derivatives upon generation of C3 ′ radicals (without O3′); whereas

  2'-氯-2'-脱氧核苷 5'二磷酸的 H3' 离子生成 C3' 自由基被提议 2a,c 引发反应，导致 RDPR 失活。6 氯化物的自发损失和 OH3 ' 质子向谷氨酸的转移将产生 2'-脱氧-3'-酮核苷酸中间体，而不涉及 R1 上的半胱氨酸对。2a,c 连续消除（H2'/碱基和 H4'/焦磷酸盐）会产生迈克尔受体 2-亚甲基-3(2 H)-呋喃酮，这会影响酶的共价失活。7 我们最近展示了一种可能产生迈克尔受体的机制替代方案，该替代方案涉及从模型 2' 取代核苷的 C2' 中丢失一个自由基，而不是一个阴离子物质。8,9 因此，处理 2'-（叠氮、溴、氯、碘、或甲硫基）核苷 3 '-硫代碳酸酯与三丁基锡烷/AIBN 导致 2 ' 取代基丢失，作为假定的自由基，在生成 C3 ' 自由基后得到 2 ',3'-二脱氢-2',3' 双脱氧衍生物（没有O3'); 而具有 2 '-氟或 2'-O-（甲磺酰基或甲苯磺酰基）取代基的