2-O-(benzoyl)-1,6-anhydro-3,4-dideoxy-β-D-erythro-hex-3-enopyranose | 67307-86-2

• 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-O-(benzoyl)-1,6-anhydro-3,4-dideoxy-β-D-erythro-hex-3-enopyranose
• 英文别名: 1,6-anhydro-2-O-benzoyl-3,4-dideoxy-β-D-erythro-hex-3-enopyranose；1,6-anhydro-3,4-dideoxy-2-O-(benzoyl)-beta-D-erythro-hex-3-enopyranose；[(1S,4R,5R)-6,8-dioxabicyclo[3.2.1]oct-2-en-4-yl] benzoate
• CAS: 67307-86-2
• 化学式: C₁₃H₁₂O₄
• 分子量: 232.236
• InChiKey: PCUIWYHIKRMCJR-DMDPSCGWSA-N

物化性质

• 沸点：
  348.5±42.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-O-(benzoyl)-1,6-anhydro-3,4-dideoxy-β-D-erythro-hex-3-enopyranose 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 1.5h， 以98.6%的产率得到1,6-anhydro-3,4-dideoxy-β-D-erythro-hex-3-enopyranose
  参考文献：
  名称：

  Synthesis of D-Allosan from Levoglucosenone

  摘要：

  The stereoselective reduction and cis-dihydroxylation of levoglucosenone (1,6-anhydro-3,4-dideoxy-beta-D-glycero-hex-3-enopyranos-2-ulose), gave D-allosan (1,6-anhydro-beta-D-allopyranose) in high yield.

  DOI：

  10.3987/com-91-5872
• 作为产物：
  描述：

  左旋葡萄糖酮 、 alkaline earth salt of/the/ methylsulfuric acid 在 sodium tetrahydroborate 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 48.17h， 生成 2-O-(benzoyl)-1,6-anhydro-3,4-dideoxy-β-D-erythro-hex-3-enopyranose
  参考文献：
  名称：

  Synthesis of Methylene-Expanded 2‘,3‘-Dideoxyribonucleosides

  摘要：

  A method for the preparation of methylene-expanded 2',3'-dideoxyribonucleosides is reported. The very inexpensive starting material levoglucosenone 8 was converted into the known mixture of alcohols 12ab which were converted into the required silyl ether alcohol 26 in six steps via either of two routes. The first involved a one-step acetylation and opening of the anhydro sugar bridge to give the triacetates 20ab which were reduced with triethylsilane and silyl triflate to afford the diacetates 21ab, both of which gave 26 after further functional group conversions. The second route entailed a simple acetylation of 12ab followed by reduction with triethylsilane and silyl triflate to give the monoacetates 19ab, both converted via straightforward chemistry into 26. Mesylation of the alcohol of 26 furnished the mesylate 27. Alkylation of adenine with the mesylate 27 afforded the silyl ether 28 which was deprotected to give the desired modified dideoxy nucleoside 7a. Alkylation of 2,6-diaminopurine 38 with the mesylate gave the protected diaminopurine nucleoside 39. Upon acetylation, it produced a mixture of di- and monoacetates 40-41, the latter of which was transformed into the desired guanosine analogue 7e. Thus, two new nucleoside analogues 7ae were prepared from levoglucosenone 8.

  DOI：

  10.1021/jo980436l

文献信息

• Method of manufacturing D-allosan
  申请人：Japan Tobacco Inc.

  公开号：US05457192A1

  公开（公告）日：1995-10-10

  The carbonyl group at the 2-position of levoglucosenone is reduced to obtain a hydroxyl group having a .beta.-configuration. The hydroxyl group having a .beta.-configuration is reversed to an .alpha.-configuration, and hydroxyl groups are added at the 3- and 4-positions in a cis-.alpha. form. Finally, the protective group of the hydroxyl group at the 2-position is eliminated. The reduction of the carbonyl group at the 2-position can be performed such that the levoglucosenone is reacted with aluminum lithium hydride or sodium boron hydride in an appropriate solvent. Reversion of the hydroxyl group having a .beta.-configuration can be performed by the Mitsunobu method or a method having a mesylation step and a step using cesium acetate. The addition of the hydroxyl groups to the 3-and 4-positions in the cis form can be performed by oxidizing the double bond across the 3- and 4-positions with an appropriate oxidizing agent. The elimination of the protective group of the hydroxyl group at the 2-position can be performed under basic conditions in accordance with normal methods. According to the method of the present invention, D-allosan can be obtained stereoselectively in high yield via a smaller number of steps than that of the conventional synthesis method.

  在得到一个具有β-构型的羟基团之后，对蔗糖醛酮的2位上的羰基团进行还原。将具有β-构型的羟基团转变为α-构型，然后以顺式α形式在3位和4位加入羟基团。最后，消除2位处羟基团的保护基团。对2位处羰基团的还原可以通过将蔗糖醛酮与适当溶剂中的铝锂氢化物或硼氢化钠反应来完成。具有β-构型的羟基团的转变可以通过Mitsunobu方法或包含甲磺酰化步骤和使用乙酸铯的方法来完成。以顺式形式在3位和4位加入羟基团可以通过适当的氧化剂氧化3位和4位之间的双键来完成。2位处羟基团的保护基团的消除可以根据常规方法在碱性条件下完成。根据本发明的方法，可以通过比传统合成方法更少的步骤高产率地立体选择性地获得D-阿洛三糖。
• PROCESS FOR PRODUCING D-ALLOSAN
  申请人：Japan Tobacco Inc.

  公开号：EP0530367A1

  公开（公告）日：1993-03-10

  A process for producing D-allosan (IV) from levoglucosenone (I) in a high yield, which comprises reducing the 2-carbonyl group of levoglucosenone, inverting the configuration of the resultant hydroxyl group from α to β, protecting it by acylation to give a compound (III), conducting α-cis addition of two hydroxyl groups to the double bond of the compound (III), and removing the protective group.

  一种以左旋葡烯酮 (I) 为原料高产制备 D-allosan (IV) 的工艺，该工艺包括还原左旋葡烯酮的 2-羰基，将所得羟基的构型从 α 反转为 β，通过酰化作用对其进行保护，得到化合物 (III)，将两个羟基与化合物 (III) 的双键进行 α-顺式加成，然后除去保护基。
• US5457192A
  申请人：——

  公开号：US5457192A

  公开（公告）日：1995-10-10
• Synthesis of D-Allosan from Levoglucosenone
  作者：Katsuya Matsumoto、Takashi Ebata、Koshi Koseki、Hiroshi Kawakami、Hajime Matsushita

  DOI：10.3987/com-91-5872

  日期：——

  The stereoselective reduction and cis-dihydroxylation of levoglucosenone (1,6-anhydro-3,4-dideoxy-beta-D-glycero-hex-3-enopyranos-2-ulose), gave D-allosan (1,6-anhydro-beta-D-allopyranose) in high yield.
• Synthesis of Methylene-Expanded 2‘,3‘-Dideoxyribonucleosides
  作者：Michael E. Jung、Mehrak Kiankarimi

  DOI：10.1021/jo980436l

  日期：1998.11.1

  A method for the preparation of methylene-expanded 2',3'-dideoxyribonucleosides is reported. The very inexpensive starting material levoglucosenone 8 was converted into the known mixture of alcohols 12ab which were converted into the required silyl ether alcohol 26 in six steps via either of two routes. The first involved a one-step acetylation and opening of the anhydro sugar bridge to give the triacetates 20ab which were reduced with triethylsilane and silyl triflate to afford the diacetates 21ab, both of which gave 26 after further functional group conversions. The second route entailed a simple acetylation of 12ab followed by reduction with triethylsilane and silyl triflate to give the monoacetates 19ab, both converted via straightforward chemistry into 26. Mesylation of the alcohol of 26 furnished the mesylate 27. Alkylation of adenine with the mesylate 27 afforded the silyl ether 28 which was deprotected to give the desired modified dideoxy nucleoside 7a. Alkylation of 2,6-diaminopurine 38 with the mesylate gave the protected diaminopurine nucleoside 39. Upon acetylation, it produced a mixture of di- and monoacetates 40-41, the latter of which was transformed into the desired guanosine analogue 7e. Thus, two new nucleoside analogues 7ae were prepared from levoglucosenone 8.