Methyl 3-deoxy-7,8-O-(1-methylethylidene)-α-D-manno-octos-2-ulo-2,6-pyranosonic acid | 119948-01-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 3-deoxy-7,8-O-(1-methylethylidene)-α-D-manno-octos-2-ulo-2,6-pyranosonic acid
• 英文别名: (2R,4R,5R,6S)-6-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-4,5-dihydroxy-2-methoxyoxane-2-carboxylic acid
• CAS: 119948-01-5
• 化学式: C₁₂H₂₀O₈
• 分子量: 292.286
• InChiKey: OJPHODMXCSELQH-ZTVJRRTOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.92
• 重原子数：
  20.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  114.68
• 氢给体数：
  3.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  Methyl 3-deoxy-7,8-O-(1-methylethylidene)-α-D-manno-octos-2-ulo-2,6-pyranosonic acid 在 Dowex 50W (H⁺) 作用下， 以 水 为溶剂， 反应 1.5h， 以44%的产率得到3-Deoxy-α-D-manno-2-octulopyranosonic acid ammonium salt
  参考文献：
  名称：

  The furan approach to oxygenated natural products. Total synthesis of (+)-KDO

  摘要：

  A de novo asymmetric synthesis of the higher monosaccharide 3-deoxy-D-manno-2-octulosonic acid, (+)-KDO (1), was completed in 12 steps starting from furan and isopropylidene-D-glyceraldehyde. The synthesis commenced with the conversion of furan (4) into the protected furfuryl carbinol 5 by the highly stereoselective addition of 2-lithiofuran to isopropylidene-D-glyceraldehyde and subsequent trapping of the intermediate alkoxide. Metalation of 5 followed by alkylation with benzyl chloromethyl ether and hydroxyl deprotection then provided 9 in a single operation. The key transformation of the synthesis entailed sequential oxidative processing of 9 with t-BuOOH in the presence of a catalytic amount of VO(acac)2 and O-methylation of the intermediate hemiacetal moiety to furnish the alpha-methyl glycoside 12 as the major product. Stereoselective 1,2-reduction of 12 using K-Selectride (Aldrich) gave the allylic alcohol 15, which was elaborated to 20 by electrophile-induced cyclization of the allylic carbamate 19. Refunctionalization of 20 proceeded in a straightforward fashion by a process involving reductive removal of iodide at C(3) and the benzyl protecting group at C(1) to furnish 23. Oxidation of the intermediate primary alcohol moiety at C(1) of 23 and deprotection of the remaining hydroxyl functions delivered (+)-KDO (1).

  DOI：

  10.1021/jo00023a028
• 作为产物：
  描述：

  (2R)-2-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-hydroxy-6-(phenylmethoxymethyl)pyran-3-one 在 W-2 Raney nickel sodium hydroxide 、 sodium tetrahydroborate 、 草酰氯 、 偶氮二异丁腈 、 iodonium di(2,4,6-trimethylpyridine) perchlorate 、 氢气 、 三正丁基氢锡 、 sodium carbonate 、 二甲基亚砜 、 三乙胺 、 silver(l) oxide 作用下， 以 乙醇 、 甲苯 、 乙腈 为溶剂， -78.0~25.0 ℃ 、448.16 kPa 条件下， 反应 90.25h， 生成 Methyl 3-deoxy-7,8-O-(1-methylethylidene)-α-D-manno-octos-2-ulo-2,6-pyranosonic acid
  参考文献：
  名称：

  The furan approach to oxygenated natural products. Total synthesis of (+)-KDO

  摘要：

  A de novo asymmetric synthesis of the higher monosaccharide 3-deoxy-D-manno-2-octulosonic acid, (+)-KDO (1), was completed in 12 steps starting from furan and isopropylidene-D-glyceraldehyde. The synthesis commenced with the conversion of furan (4) into the protected furfuryl carbinol 5 by the highly stereoselective addition of 2-lithiofuran to isopropylidene-D-glyceraldehyde and subsequent trapping of the intermediate alkoxide. Metalation of 5 followed by alkylation with benzyl chloromethyl ether and hydroxyl deprotection then provided 9 in a single operation. The key transformation of the synthesis entailed sequential oxidative processing of 9 with t-BuOOH in the presence of a catalytic amount of VO(acac)2 and O-methylation of the intermediate hemiacetal moiety to furnish the alpha-methyl glycoside 12 as the major product. Stereoselective 1,2-reduction of 12 using K-Selectride (Aldrich) gave the allylic alcohol 15, which was elaborated to 20 by electrophile-induced cyclization of the allylic carbamate 19. Refunctionalization of 20 proceeded in a straightforward fashion by a process involving reductive removal of iodide at C(3) and the benzyl protecting group at C(1) to furnish 23. Oxidation of the intermediate primary alcohol moiety at C(1) of 23 and deprotection of the remaining hydroxyl functions delivered (+)-KDO (1).

  DOI：

  10.1021/jo00023a028

文献信息

• The furan approach to higher monosaccharides. A concise total synthesis of (+)-KDO
  作者：Stephen F. Martin、Paul W. Zinke

  DOI：10.1021/ja00188a060

  日期：1989.3