3-O-benzoyl-4-O-benzyl-1,2-O-isopropylidene-5-O-methanesulfonyl-β-D-fructopyranose | 340969-78-0

• 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: 3-O-benzoyl-4-O-benzyl-1,2-O-isopropylidene-5-O-methanesulfonyl-β-D-fructopyranose
• 英文别名: [(5S,6S,7S,8R)-2,2-dimethyl-8-methylsulfonyloxy-7-phenylmethoxy-1,3,10-trioxaspiro[4.5]decan-6-yl] benzoate
• CAS: 340969-78-0
• 化学式: C₂₄H₂₈O₉S
• 分子量: 492.547
• InChiKey: ZSQVUKOWKNZAFS-YOEKFXIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  115
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3-O-benzoyl-4-O-benzyl-1,2-O-isopropylidene-5-O-methanesulfonyl-β-D-fructopyranose 在 palladium on activated charcoal 、 镍 咪唑 、 盐酸 、 sodium azide 、 四丁基氟化铵 、 氢气 、 sodium methylate 、 sodium hydride 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 20.0~80.0 ℃ 、345.0 kPa 条件下， 反应 94.0h， 生成 2,5-二(羟基甲基)-3,4-吡咯烷二醇
  参考文献：
  名称：

  A practical route to partially protected pyrrolidines as precursors for the stereoselective synthesis of alexines

  摘要：

  Either 3-O-benzoyl- (2a) or 3-O-benzyl-1,2-O-isopropylidene-beta-D-fructopyranose (2b) were regioselectively O-benzylated at C-4 to give 4a and 4b, respectively, which were transformed into 5-azido-3-O-benzoyl-4-O-benzyl- (6a) and 5-azido-3,4-di-O-benzyl-5-deoxy-1,2-O-isopropylidene-alpha-L-sorbopyranose (6b) by nucleophilic displacement of the corresponding 5-O-mesyl derivatives 5a and 5b by sodium azide in DMF, respectively. Compound 6b was also prepared from 4b in one step by the Mitsunobu methodology. Deacetonation of 6a and 6b gave the partially protected free azidouloses 8a and 8b, respectively, that were protected as their 1-O-TBDPS derivatives 9a and 9b. Hydrogenation of 9b over Raney nickel gave stereoselectively (2R,3R,4R,5S)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (12) which was identified by transformation into the well known (2R,3R,4R,5S)-3,4-dihydroxy-2,5-bis(hydroxymethyl)pyrrolidine (1, DGDP).

  DOI：

  10.1016/s0008-6215(00)00319-0
• 作为产物：
  描述：

  甲基磺酰氯 、 3-O-benzoyl-4-O-benzyl-1,2-O-isopropylidene-β-D-fructopyranose 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到3-O-benzoyl-4-O-benzyl-1,2-O-isopropylidene-5-O-methanesulfonyl-β-D-fructopyranose
  参考文献：
  名称：

  A practical route to partially protected pyrrolidines as precursors for the stereoselective synthesis of alexines

  摘要：

  Either 3-O-benzoyl- (2a) or 3-O-benzyl-1,2-O-isopropylidene-beta-D-fructopyranose (2b) were regioselectively O-benzylated at C-4 to give 4a and 4b, respectively, which were transformed into 5-azido-3-O-benzoyl-4-O-benzyl- (6a) and 5-azido-3,4-di-O-benzyl-5-deoxy-1,2-O-isopropylidene-alpha-L-sorbopyranose (6b) by nucleophilic displacement of the corresponding 5-O-mesyl derivatives 5a and 5b by sodium azide in DMF, respectively. Compound 6b was also prepared from 4b in one step by the Mitsunobu methodology. Deacetonation of 6a and 6b gave the partially protected free azidouloses 8a and 8b, respectively, that were protected as their 1-O-TBDPS derivatives 9a and 9b. Hydrogenation of 9b over Raney nickel gave stereoselectively (2R,3R,4R,5S)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (12) which was identified by transformation into the well known (2R,3R,4R,5S)-3,4-dihydroxy-2,5-bis(hydroxymethyl)pyrrolidine (1, DGDP).

  DOI：

  10.1016/s0008-6215(00)00319-0

文献信息

• Polyhydroxylated pyrrolidines. Part 4: Synthesis from d-fructose of protected 2,5-dideoxy-2,5-imino-d-galactitol derivatives
  作者：Isidoro Izquierdo、María T. Plaza、Miguel Rodríguez、Juan A. Tamayo、Alicia Martos

  DOI：10.1016/j.tet.2005.12.023

  日期：2006.3

  configuration at C(3). Compound 8 was treated with lithium azide yielding 5-azido-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-α-l-tagatopyranose (9) that was transformed into the related 3,4-di-O-benzyl derivative 10. Cleavage of the acetonide in 10 to give 11, followed by regioselective 1-O-pivaloylation to 12 and subsequent catalytic hydrogenation gave (2R,3S,4R,5S)-3,4-dibenzyloxy-2,5-bis(hydroxymethyl

  容易获得的3 - O-苯甲酰基-4- O-苄基-1,2- O-异亚丙基-5- O-甲磺酰基-β-d-果糖基吡喃糖（5）直接转化为其d- psico差向异构体（8），后Ó -debenzoylation随后的氧化和还原，这引起了构造的反转在C（3）。用叠氮化锂处理化合物8，得到5-叠氮基-4 - O-苄基-5-脱氧-1,2 - O-异亚丙基-α-1-tag-吡喃葡萄糖（9），将其转化为相关的3,4-二-邻苄基衍生物10。将丙酮化物在10中裂解，得到11，然后进行区域选择性1- O-聚戊二醛化至12，然后进行催化氢化，得到（2 R，3 S，4 R，5 S）-3,4-二苄氧基-2,5-bis （羟甲基）-2'- O-吡咯烷基吡咯烷（13）。O-脱酰基为对称的吡咯烷14后，可以确定13的立体化学。14的总脱保护得到2，5-亚氨基-2，5-二脱氧-d-半乳糖醇（15，DGADP）。