2,3-Anhydro-5-O-benzyl-β-D-ribofuranoside de methyle | 20535-09-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3-Anhydro-5-O-benzyl-β-D-ribofuranoside de methyle
• 英文别名: Methyl 2,3-anhydro-5-O-benzyl-β-D-ribofuranoside；(1R,2R,4R,5R)-2-methoxy-4-(phenylmethoxymethyl)-3,6-dioxabicyclo[3.1.0]hexane
• CAS: 20535-09-5
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: XAOAXRUYUGVVRU-FDYHWXHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  40.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,3-Anhydro-5-O-benzyl-β-D-ribofuranoside de methyle 在 咪唑 、 盐酸 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 正丁基锂 、 copper(I) bromide dimethylsulfide complex 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 calcium carbonate 、 mercury dichloride 作用下， 以 四氢呋喃 、 正己烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 91.16h， 生成 (αS,1'R,2'S)-α-[1-methyl-2-[(tert-butyldimethylsilyl)-oxy]-3-phenylmethoxy-propyl]-5-hydroxymethyl-2-furaneethanol
  参考文献：
  名称：

  FK-506的全合成。第1部分：C16–C34片段的构建

  摘要：

  C23–C27 1,3-二醇是通过Brown的crotylation-osmylation或区域和D-xylofuranose衍生的2,3-anhydro-β-rifurfuranoside的立体选择性开口而构建的。路易斯酸用受保护的硫代糠醛醇催化环氧化物开环，然后氧化螺环缩酮化，将C21–C24螺缩酮建立为掩蔽的α'-烯丙基醛醇。C19-C20三取代的烯烃是通过锆催化的碳铝化反应合成的-用较高级的铜酸盐原位进行金属转移，然后将立体选择性的共轭物加成螺碳烯酮。C27-C28三取代烯烃是通过将铜酸甲酯与烯醇三酯偶联（通过声波作用）或通过C17-醛与C28-乙烯基溴化镁之间的直接偶联而形成的。

  DOI：

  10.1016/s0040-4020(97)00865-x
• 作为产物：
  描述：

  methyl 2,3-anhydro-5-O-benzyl-α-D-ribofuranoside 在 三氟化硼乙醚 作用下， 以 甲醇 为溶剂， 以78%的产率得到2,3-Anhydro-5-O-benzyl-β-D-ribofuranoside de methyle
  参考文献：
  名称：

  FK-506的全合成。第1部分：C16–C34片段的构建

  摘要：

  C23–C27 1,3-二醇是通过Brown的crotylation-osmylation或区域和D-xylofuranose衍生的2,3-anhydro-β-rifurfuranoside的立体选择性开口而构建的。路易斯酸用受保护的硫代糠醛醇催化环氧化物开环，然后氧化螺环缩酮化，将C21–C24螺缩酮建立为掩蔽的α'-烯丙基醛醇。C19-C20三取代的烯烃是通过锆催化的碳铝化反应合成的-用较高级的铜酸盐原位进行金属转移，然后将立体选择性的共轭物加成螺碳烯酮。C27-C28三取代烯烃是通过将铜酸甲酯与烯醇三酯偶联（通过声波作用）或通过C17-醛与C28-乙烯基溴化镁之间的直接偶联而形成的。

  DOI：

  10.1016/s0040-4020(97)00865-x

文献信息

• Vinyl sulfone- and vinyl sulfoxide-modified tetrahydrofurans: a preliminary account of the enantiomeric synthesis of and diastereoselectivity of addition to new classes of Michael acceptors
  作者：Debanjana Dey、Atanu Bhaumik、Tanmaya Pathak

  DOI：10.1016/j.tet.2013.07.093

  日期：2013.10

  methods reported so far for the synthesis of this type of compounds. Hydroxymethylene group is sufficient to impose diastereoselectivity on the addition of a wide range of nucleophiles to vinyl sulfone-modified tetrahydrofurans. The benzyl protected hydroxymethylene group also suppresses the influence of chirally pure sulfoxides as two diastereomeric vinyl sulfoxide-modified tetrahydrofurans afforded the

  对映异构体纯的2-羟基亚甲基取代的-2,5-二氢-3-（芳基磺酰基） - 和2-羟基亚甲基取代的-2,5-二氢-3-（芳基亚磺酰基）-furans已经从容易获得碳水化合物衍生物制备的第一次。用于访问这两个砜和亚砜的策略是更有效的比方法这种类型的化合物的合成报告为止。羟基亚甲基足以强加于除了大范围的亲核试剂，以乙烯基砜改性的非对映选择性四氢呋喃。的苄基保护的羟基亚甲基也抑制手性纯的亚砜作为在C-3和C-4，得到具有相同的配置的迈克尔加成物的非对映2乙烯基亚砜改性的四氢呋喃的影响; 这是通过氧化加合物而建立的，这被认为是等同于通过将相同的亲核试剂，以相应的乙烯基砜制得的产品。这些高活性的迈克尔受体可被视为一个新的除了有志于四氢呋喃的功能化合成化学家的兵工厂。
• Synthesis of anomerically pure vinyl sulfone-modified pent-2-enofuranosides and hex-2-enopyranosides: a group of highly reactive Michael acceptors for accessing carbohydrate based synthons
  作者：Aditya Kumar Sanki、Tanmaya Pathak

  DOI：10.1016/s0040-4020(03)01059-7

  日期：2003.9

  from the derivatives of d-xylose. For the synthesis of α- and β-anomers of vinyl sulfone-modified hex-2-enopyranosides, a d-glucose derivative was selected over a d-allose derivative as the starting material because the former almost exclusively produced the required methyl pyranosides whereas the latter produced a mixture. All sulfides were converted to vinyl sulfone-modified carbohydrates by the sequential

  乙烯基砜改性的戊-2-烯呋喃糖苷的苄基或三苯甲基保护的α-和β-端基异构体的合成已通过适当掩蔽的甲基α - lyxo呋喃糖基环氧化合物或甲基β-核糖呋喃糖基环氧化合物的开环而引发。或通过苄基保护的3- O-甲苯磺酰基木糖呋喃糖苷和3- O-甲磺酰基核糖呋喃糖苷中离去基团的亲核取代被p-硫代甲酚。在后一组原料的情况下，α-和β-甲基糖苷仅由d-木糖的衍生物以几乎相等的比例形成。对于乙烯基砜改性的hex-2-enopyranosides的α和β端基异构体的合成，选择d-葡萄糖衍生物而不是d-阿洛糖衍生物作为起始原料，因为前者几乎只能生产所需的甲基吡喃糖苷，而后者产生了混合物。通过顺序应用氧化，甲磺酰化和碱诱导的消除反应，将所有硫化物均转化为乙烯基砜改性的碳水化合物。
• Enantiopure 1,4,5-Trisubstituted 1,2,3-Triazoles from Carbohydrates: Applications of Organoselenium Chemistry
  作者：Atanu Bhaumik、Supravat Samanta、Tanmaya Pathak

  DOI：10.1021/jo5009564

  日期：2014.8.1

  A wide range of stable vinyl selenone-modified furanosides has been synthesized for the first time. These 2 pi-partners undergo 1,3-dipolar cycloaddition reactions with a wide range of organic azides to afford enantiopure trisubstituted triazoles. Furanosyl rings opened up during triazole synthesis to generate polyfunctionalized molecules, ready to undergo further transformations. This strategy is one of the most convenient methods for the synthesis of enantiopure 1,4,5-trisubstituted 1,2,3-triazoles where the chiral components are attached to C-4 or C-5 position of triazole ring. These triazoles are formed in a regioselective manner, and several pairs of regioisomeric triazoles have also been synthesized. The approach affords densely functionalized triazoles, which are amenable to further modifications because of the presence of aldehyde and hydroxyl groups. This powerful and practical route adds to the arsenals of chemists and biologists interested in the synthesis and applications of triazoles.
• Fluorination by anchimeric assistance of a diallylamino group: application to the synthesis of some methyl aminofluoropentofuranosides
  作者：Marie-Béatrice Giudicelli、Marie-Agnès Thomé、Dominique Picq、Daniel Anker

  DOI：10.1016/0008-6215(93)84057-d

  日期：1993.10

  Methyl 2,3-trans-dialkylaminofluoro-alpha(or beta)-D-pentofuranosides were prepared by fluorination wherein the dialkylamino, group assists the replacement of a trans-vicinal mesylate. Whatever the location of the dialkylamino group (alpha or beta face of the ring), the regioselectivity of fluorination depends mainly on the alpha or beta orientation of the anomeric methoxyl group. The use of a diallylamino substituent led to methyl 3-amino-2,3-dideoxy-2-fluoro-beta-D-xylofuranoside, methyl 2-amino-2,3-dideoxy-3-fluoro-alpha-D-arabinofuranoside, methyl 2-amino-2,3-dideoxy-3-fluoro-beta-D-xylofuranoside, and methyl 3-amino-2,3-dideoxy-2-fluoro-alpha-D-arabinofuranoside. Attempts to obtain 2(or 3),5-difluoro analogues staring from corresponding dimesylates gave only disappointing results.
• Synthese et equilibre thermodynamique des huit 5-O-benzyl-2- (ou 3)- dimethylamino-3 (ou 2)-O-mesyl-α (ou β)-D- (ou ) - furanosides de methyle
  作者：Marie-Béatrice Giudicelli、Marie-Agnès Thomé、Dominique Picq、Daniel Anker

  DOI：10.1016/s0040-4020(01)90122-x

  日期：1992.1

  Regioselectivity of the opening of 2,3-anhydrofuranosides 1 (alpha and beta) and 2 (alpha and beta) by dimethylamine (and by ammonia for 1) has been determined. Thermic stability of the eight corresponding vic-dimethylaminomesylates 11-14 (alpha and beta) in CD3CN and C6D6 has been studied by H-1 NMR : in each case steric hindrance seems to be the determinant factor of the four thermodynamic equilibria 11 reversible 12 (alpha and beta) and 13 reversible 14 (alpha and beta); aziridinium ions are assumed to be formed as intermediates and one of them has been effectively observed.