Methyl 2,6-dideoxy-3-C-methyl-α-L-xylo-hexopyranoside | 6752-55-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 2,6-dideoxy-3-C-methyl-α-L-xylo-hexopyranoside
• 英文别名: methyl 2,6-dideoxy-3-C-methyl-L-xylo-hexopyranoside；Methyl-β-oxenosid；3t,4c-Dihydroxy-6t-methoxy-2r,4t-dimethyl-tetrahydropyran；(2S,3R,4R,6S)-6-methoxy-2,4-dimethyloxane-3,4-diol
• CAS: 6752-55-2；13322-78-6；18424-67-4；19272-31-2；19272-32-3；22596-19-6；38411-52-8；40983-29-7；40983-30-0；56782-16-2；73712-09-1；98168-05-9；98168-06-0；98168-08-2；98168-09-3；107657-25-0；148023-25-0
• 化学式: C₈H₁₆O₄
• 分子量: 176.213
• InChiKey: YLMFFJPPIFKCBQ-RULNZFCNSA-N

物化性质

• 熔点：
  55 °C
• 沸点：
  272.5±40.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  methyl 2-deoxy-3-O-benzyl-β-D-erythro-pentofuranoside 在 吡啶 、 咪唑 、 chromium(VI) oxide 、 盐酸 、 氢氧化钾 、 ammonium hydroxide 、 N-溴代丁二酰亚胺(NBS) 、 cerium(III) chloride 、 草酰氯 、 乙酸酐 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 calcium carbonate 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 二氯甲烷 、 苯 为溶剂， 反应 115.42h， 生成 Methyl 2,6-dideoxy-3-C-methyl-α-L-xylo-hexopyranoside
  参考文献：
  名称：

  Stereoselectivity of Addition of Organometallic Reagents to Pentodialdo-1,4-furanoses: Synthesis of L-Axenose and D-Evermicose from a Common Intermediate

  摘要：

  The additions of organometallic reagents to two pentodialdo-1,4-furanosides (methyl 3-O-benzyl-2-deoxy-alpha-D-erythro-pentofuranoside and its beta-anomer) were carried out under a variety of experimental conditions. Methylmagnesium halides, methyllithium, methylcerium and the organotitanium reagent MeTi(OiPr)(3) were reacted with the pentodialdo-1,4-furanosides in an effort to determine if the stereoselectivity of addition to the formyl group is the result of chelation or nonchelation control and to determine the effect of anomeric configuration. The stereochemistry of the products was assigned by NMR methods and correlation with known compounds synthesized previously. The stereoselectivity of addition depends on the configuration at the anomeric center of the dialdose, with the beta-anomer giving mainly the product of a non-chelation-controlled addition and the beta-anomer giving the opposite stereoselectivity. The major product obtained from the beta-anomer was utilized as a key intermediate in the synthesis of two branched-chain carbohydrates, axenose and evermicose, found in antibiotics. Methylcerium additions are the most efficient method for introducing the branching methyl group in a 2-deoxyfuranosid-3-ulose.

  DOI：

  10.1021/jo00106a035

文献信息

• Diastereoselective Additions of Allylmetal Reagents to Free and Protected <i>syn</i>-<b>α,β</b>-Dihydroxyketones Enable Efficient Synthetic Routes to Methyl Trioxacarcinoside A
  作者：Daniel J. Smaltz、Jakub Švenda、Andrew G. Myers

  DOI：10.1021/ol300377a

  日期：2012.4.6

  Two routes to the 2,6-dideoxysugar methyl trioxacarcinoside A are described. Each was enabled by an apparent α-chelation-controlled addition of an allylmetal reagent to a ketone substrate containing a free α-hydroxyl group and a β-hydroxyl substituent, either free or protected as the corresponding di-tert-butylmethyl silyl ether. Both routes provide practical access to gram quantities of trioxacarcinose

  描述了 2,6-二脱氧糖甲基三恶癌苷 A 的两条路线。每一种都是通过将烯丙基金属试剂以明显的α-螯合控制添加到含有游离α-羟基和β-羟基取代基的酮底物上来实现的，该取代基可以是游离的或被保护为相应的二叔丁基甲基甲硅烷基醚。两种途径都提供了以适合糖苷偶联反应的形式实际获得克量的三氧癌糖A的途径。
• Antitumor agents LL-D49194 alpha 1, LL-D49194 beta, LL-D49194 beta 2, LL-D49194 upsilon, LL-D49194 delta, LL-D49194 epsilon, LL-D49194 zeta, and LL-D49194 eta
  申请人：AMERICAN CYANAMID COMPANY

  公开号：EP0157203A2

  公开（公告）日：1985-10-09

  Antitumor agents LL-D49194αa, LL-D49194β1, LL-D49194p2, LL-D49194β3, LL-D49194y, LL-D49194δ, LL-D49194ε, LL-D49194ζ, LL-D49194η, LL-D49194ω1, LL-D49194ω2 and LL-D49194ω3.

  抗肿瘤药 LL-D49194αa、LL-D49194β1、LL-D49194p2、LL-D49194β3、LL-D49194y、LL-D49194δ、LL-D49194ε、LL-D49194ζ、LL-D49194η、LL-D49194ω1、LL-D49194ω2 和 LL-D49194ω3。
• Synthesis of Methyl Axenoside and Methyl 3-epi-Axenoside via Ate-Mediated Allylic Substitution (AMAS)
  作者：D. McQuade、Brian Ondrusek

  DOI：10.1055/s-0033-1339116

  日期：——

  An ate-mediated allylic substitution (AMAS) of vinylboronates is utilized in the divergent syntheses of the sugars methyl axenoside and methyl 3-epi-axenoside. Other key steps of the synthesis involve the dihydroxylation of the resulting allylic alcohol and selective oxidation of the resultant diol. Benefits of this methodology are also discussed.
• US4626503A
  申请人：——

  公开号：US4626503A

  公开（公告）日：1986-12-02
• Stereoselectivity of Addition of Organometallic Reagents to Pentodialdo-1,4-furanoses: Synthesis of L-Axenose and D-Evermicose from a Common Intermediate
  作者：Robert M. Giuliano、Frank J. Jr. Villani

  DOI：10.1021/jo00106a035

  日期：1995.1

  The additions of organometallic reagents to two pentodialdo-1,4-furanosides (methyl 3-O-benzyl-2-deoxy-alpha-D-erythro-pentofuranoside and its beta-anomer) were carried out under a variety of experimental conditions. Methylmagnesium halides, methyllithium, methylcerium and the organotitanium reagent MeTi(OiPr)(3) were reacted with the pentodialdo-1,4-furanosides in an effort to determine if the stereoselectivity of addition to the formyl group is the result of chelation or nonchelation control and to determine the effect of anomeric configuration. The stereochemistry of the products was assigned by NMR methods and correlation with known compounds synthesized previously. The stereoselectivity of addition depends on the configuration at the anomeric center of the dialdose, with the beta-anomer giving mainly the product of a non-chelation-controlled addition and the beta-anomer giving the opposite stereoselectivity. The major product obtained from the beta-anomer was utilized as a key intermediate in the synthesis of two branched-chain carbohydrates, axenose and evermicose, found in antibiotics. Methylcerium additions are the most efficient method for introducing the branching methyl group in a 2-deoxyfuranosid-3-ulose.