2-Deoxy-4,5:6,7-di-O-isopropylidene-D-manno-heptose trimethylene dithioacetal | 148324-14-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Deoxy-4,5:6,7-di-O-isopropylidene-D-manno-heptose trimethylene dithioacetal
• 英文别名: 1,(2R):(3R,4R)-diisopropylidenedioxy-(5R)-hydroxy-7,7-propylenedithioheptane；(1R)-1-[(4R,5R)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]-2-(1,3-dithian-2-yl)ethanol
• CAS: 148324-14-5
• 化学式: C₁₆H₂₈O₅S₂
• 分子量: 364.527
• InChiKey: NZSFYACNJNIYTG-HBJVGIJOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-Deoxy-4,5:6,7-di-O-isopropylidene-D-manno-heptose trimethylene dithioacetal 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 正丁基锂 、 Raney nickel W-2 、 sodium methylate 、 三溴化硼 、 sodium hydride 、 sodium nitrite 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 105.5h， 生成 5a-carba-1,5-anhydro-L-iditol
  参考文献：
  名称：

  From Sugars to Carbocycles. 3. Synthesis of Validatol and 4-epi-Validatol from Mannose and Glucose

  摘要：

  Validatol (4) and 4-epi-validatol (8) are synthesized from mannose and glucose, respectively. The key step in the synthesis of 4 is the base-induced intramolecular displacement reaction of the epoxy dithiane 14 to yield the six-membered carbocycle 15 exclusively.

  DOI：

  10.1021/jo00099a044
• 作为产物：
  描述：

  3,4;6,7-Di-O-isopropyliden-D-glycero-D-galacto-heptose-trimethylendithioacetal 在 lithium aluminium tetrahydride 、 硫酸 作用下， 反应 4.5h， 生成 2-Deoxy-4,5:6,7-di-O-isopropylidene-D-manno-heptose trimethylene dithioacetal
  参考文献：
  名称：

  From Sugars to Carbocycles. 2. Three- to Seven-Membered Rings from Mannose by Addition of 1,3-Dithiane Followed by Intramolecular Displacement Reaction

  摘要：

  A new methodology for the conversion of sugars to three-, four-, six-, and seven-membered rings is presented. The sequence of transformations is demonstrated with mannose (1) and involves addition of 2-lithio-1,3-dithiane to the acetonide 2 followed by elimination and reduction to the 2-deoxy-dithiane 6. Starting from this intermediate, appropriate activation (tosylate, epoxide) and protection (acetonide, methyl ether) yields 8, 18, and 23, the starting materials for carbocyclization, which are converted by nucleophile displacement to the optically active cyclopropane 9, cyclobutane 19, cyclohexane 24, and cycloheptane 25, respectively. The cyclopropyl-1,3-dithane 9 can be desulfurized to the cyclopropane 10.

  DOI：

  10.1021/jo00099a043

文献信息

• Chemoenzymatic Carbon-Carbon Bond Formation Leading to Non-carbohydrate Derivative. Stereoselective Synthesis of Pentamycin C-11-C-16 Fragment.
  作者：Masayuki SHIMAGAKI、Hiroaki MUNESHIMA、Masahide KUBOTA、Takeshi OISHI

  DOI：10.1248/cpb.41.282

  日期：——

  Chemoenzymatic formation of 8 from an aldehyde 5 and dihydroxyacetone phosphate 6 was achieved by the use of fructose 1, 6-diphosphate aldolase as a catalyst. Transformation of 8 to 20, corresponding to pentamycin C-11-C-16 fragment, was accomplished via 18a and 18b by chemical processes.

  通过使用 1，6-二磷酸果糖醛缩酶作为催化剂，醛 5 和磷酸二羟丙酮 6 在化学酶作用下生成了 8。通过化学过程 18a 和 18b 将 8 转化为 20，对应于五霉素 C-11-C-16 片段。
• From Sugars to Carbocycles. 3. Synthesis of Validatol and 4-epi-Validatol from Mannose and Glucose
  作者：Karsten Krohn、Guido Boerner、Stephan Gringard

  DOI：10.1021/jo00099a044

  日期：1994.10

  Validatol (4) and 4-epi-validatol (8) are synthesized from mannose and glucose, respectively. The key step in the synthesis of 4 is the base-induced intramolecular displacement reaction of the epoxy dithiane 14 to yield the six-membered carbocycle 15 exclusively.
• From Sugars to Carbocycles. 2. Three- to Seven-Membered Rings from Mannose by Addition of 1,3-Dithiane Followed by Intramolecular Displacement Reaction
  作者：Karsten Krohn、Guido Boerner

  DOI：10.1021/jo00099a043

  日期：1994.10

  A new methodology for the conversion of sugars to three-, four-, six-, and seven-membered rings is presented. The sequence of transformations is demonstrated with mannose (1) and involves addition of 2-lithio-1,3-dithiane to the acetonide 2 followed by elimination and reduction to the 2-deoxy-dithiane 6. Starting from this intermediate, appropriate activation (tosylate, epoxide) and protection (acetonide, methyl ether) yields 8, 18, and 23, the starting materials for carbocyclization, which are converted by nucleophile displacement to the optically active cyclopropane 9, cyclobutane 19, cyclohexane 24, and cycloheptane 25, respectively. The cyclopropyl-1,3-dithane 9 can be desulfurized to the cyclopropane 10.