methyl 4-O-acetyl-2,6-di-O-pivaloyl-α-D-ribo-hexopyranosid-3-ulose | 488820-57-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-O-acetyl-2,6-di-O-pivaloyl-α-D-ribo-hexopyranosid-3-ulose
• CAS: 488820-57-1
• 化学式: C₁₉H₃₀O₉
• 分子量: 402.442
• InChiKey: YACLPBCITREQQV-NGFQHRJXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.41
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  114.43
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  methyl 4-O-acetyl-2,6-di-O-pivaloyl-α-D-ribo-hexopyranosid-3-ulose 在 Dimethylzinc 、 锌 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 77.0h， 生成 methyl 2,6-di-O-pivaloyl-3-C-(carboxymethyl)-α-D-allopyranoside-3',3-lactone
  参考文献：
  名称：

  SYNTHETIC APPROACH TO TETRAHYDROFURAN UNITS AND FIVE-MEMBERED RING LACTONES FUSED TO HEXOPYRANOSIDES ^*

  摘要：

  A stereoselective synthesis of the miharamycin sugar moiety epimer at C-3' was accomplished in high yield starting from an appropriate (Z)-Wittig product, synthesized by Wittig reaction of a 4,6-O-benzylidene protected hexopyranosid-3-ulose with [(ethoxycarbonyl)methylene]triphenylphosphorane followed by iodine promoted isomerisation of the (E)-Wittig product formed. Reduction of the (Z)-isomer obtained in quantitative yield, cyclisation and dihydroxylation with osmium tetroxide, gave the target molecule containing a cis-fused tetrahydrofuran ring in its structure. Synhesis of five-membered rings trans-fused to the hexopyranosidic units succeeded via two different synthetic pathways. Stereoselective Reformatsky reaction of a 2,6-di-O-pivaloyl protected hexopyranosid-3-ulose, followed by cyclisation with dimethylzinc gave a 3,4-trans-fused lactone. The approach using the reaction of 2,3-and 3,4-epoxides with the dianion of phenylselenoacetic acid led to low yield but novel phenylseleno derivatives of trans-fused five-membered rings, namely a phenylselenolactone 2,3-trans-fused to a 4,6-O-benzylidenehexopyranoside and a phenylselenolactenol 3,4-trans-fused to a 6-O-pivaloyl-hexopyranoside.

  DOI：

  10.1081/car-120013489
• 作为产物：
  描述：

  乙酸酐 、 (2S,3S,5R,6R)-5-hydroxy-2-methoxy-4-oxo-6-(pivaloyloxymethyl)tetrahydro-2H-pyran-3-yl pivalate 在 吡啶 作用下， 反应 16.0h， 以93%的产率得到methyl 4-O-acetyl-2,6-di-O-pivaloyl-α-D-ribo-hexopyranosid-3-ulose
  参考文献：
  名称：

  SYNTHETIC APPROACH TO TETRAHYDROFURAN UNITS AND FIVE-MEMBERED RING LACTONES FUSED TO HEXOPYRANOSIDES ^*

  摘要：

  A stereoselective synthesis of the miharamycin sugar moiety epimer at C-3' was accomplished in high yield starting from an appropriate (Z)-Wittig product, synthesized by Wittig reaction of a 4,6-O-benzylidene protected hexopyranosid-3-ulose with [(ethoxycarbonyl)methylene]triphenylphosphorane followed by iodine promoted isomerisation of the (E)-Wittig product formed. Reduction of the (Z)-isomer obtained in quantitative yield, cyclisation and dihydroxylation with osmium tetroxide, gave the target molecule containing a cis-fused tetrahydrofuran ring in its structure. Synhesis of five-membered rings trans-fused to the hexopyranosidic units succeeded via two different synthetic pathways. Stereoselective Reformatsky reaction of a 2,6-di-O-pivaloyl protected hexopyranosid-3-ulose, followed by cyclisation with dimethylzinc gave a 3,4-trans-fused lactone. The approach using the reaction of 2,3-and 3,4-epoxides with the dianion of phenylselenoacetic acid led to low yield but novel phenylseleno derivatives of trans-fused five-membered rings, namely a phenylselenolactone 2,3-trans-fused to a 4,6-O-benzylidenehexopyranoside and a phenylselenolactenol 3,4-trans-fused to a 6-O-pivaloyl-hexopyranoside.

  DOI：

  10.1081/car-120013489

文献信息

• Synthesis of Phenylseleno Sugars from Epoxides and of α,β‐Unsaturated Carbonyl Derivatives for the Study of Their Insecticidal Activity
  作者：Amélia P. Rauter、Tana Canda、Jorge Justino、Maria I. Ismael、José A. Figueiredo

  DOI：10.1081/car-200030077

  日期：2004.12.29

  This work reports the synthesis of sugar epoxides and their derivatives obtained by reaction with the dianion of phenyl selenoacetic acid. Approaches to the introduction of alpha,beta-unsaturated carbonyl units in pyranoid systems were investigated. Preparation of a protected D-glycero-hex-3-enepyranosid-2-ulose and of a D-erythro-hex-2-enono-1,5-lactone is described. Some of the synthesized compounds possess insecticidal activity against fruit flies, house flies, and white flies.