(2R)-2-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-hydroxy-6-(phenylmethoxymethyl)pyran-3-one | 136089-34-4

• 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: (2R)-2-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-hydroxy-6-(phenylmethoxymethyl)pyran-3-one
• CAS: 136089-34-4；136172-78-6
• 化学式: C₁₈H₂₂O₆
• 分子量: 334.369
• InChiKey: DQXVZSDSDNWNCY-LNKXUWQBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  74.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2R)-2-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-hydroxy-6-(phenylmethoxymethyl)pyran-3-one 在 sodium tetrahydroborate 、 silver(l) oxide 作用下， 反应 12.0h， 生成 Methyl 3,4-dideoxy-7,8-O-(1-methylethylidene)-1-O-(phenylmethyl)-α-D-ribo-oct-3-en-2-ulopyranoside
  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：

  苄基氯甲基醚 在 叔丁基过氧化氢 、 bis(acetylacetonate)oxovanadium 、 四丁基氟化铵 、 叔丁基锂 作用下， 以 四氢呋喃 、 异辛烷 、 二氯甲烷 为溶剂， 反应 22.0h， 生成 (2R)-2-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-hydroxy-6-(phenylmethoxymethyl)pyran-3-one
  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