5-azido-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-β-D-psicopyranose | 872345-45-4

• 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: 5-azido-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-β-D-psicopyranose
• 英文别名: (5S,6R,7R,8R)-8-azido-2,2-dimethyl-7-phenylmethoxy-1,3,10-trioxaspiro[4.5]decan-6-ol
• CAS: 872345-45-4
• 化学式: C₁₆H₂₁N₃O₅
• 分子量: 335.36
• InChiKey: MEHBGQDASAWAEE-KQTLUZQSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  71.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5-azido-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-β-D-psicopyranose 在 sodium hydride 、 三苯基膦 、 三氟乙酸 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 29.0h， 生成 (3S,4R,5R)-3,4-dibenzyloxy-2',5'-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)-δ²-pyrroline
  参考文献：
  名称：

  Polyhydroxylated pyrrolidines, III. Synthesis of new protected 2,5-dideoxy-2,5-iminohexitols from d-fructose

  摘要：

  The readily available 3-O-benzoyl-4-O-benzyl-1,2-Oisopi-opylidene-beta-D-fructopyranose (6) was straightforwardly transformed into 5-azido-3-O-benzoyl-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose (8), after treatment under modified Garegg's conditions followed by reaction of the resulting 3-O-benzoyl-4-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose (7) with lithium azide in DMF O-debenzoylation at C(3) in 8, followed by oxidation and reduction caused the inversion of the configuration to afford the corresponding beta-D-psicopyranose derivative 11 that was transformed into the related 3,4-di-O-benzyl derivative 12. Cleavage of the acetonide of 12 to give 13 followed by O-tert-butyldiphenylsilylation afforded a resolvable mixture of 14 and 15. Compound 14 was transformed into (2R,3R,4S,5R)- (17) and (2R,3R,4S,5S)-3,4-dibenzyloxy-2',5'-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (18) either by a tandem Staudinger/intramolecular aza-Wittig process and reduction of the resulting intermediate 2 only into 18 by a high stereoselective catalytic hydrogenation. When 15 was subjected to the same protocol, (2S,3S,4R,5R)- (21) and (2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (22) were obtained, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.09.043
• 作为产物：
  描述：

  5-azido-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-β-D-fructopyranose 在 sodium tetrahydroborate 、 戴斯-马丁氧化剂 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 5-azido-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-β-D-psicopyranose
  参考文献：
  名称：

  Polyhydroxylated pyrrolidines, III. Synthesis of new protected 2,5-dideoxy-2,5-iminohexitols from d-fructose

  摘要：

  The readily available 3-O-benzoyl-4-O-benzyl-1,2-Oisopi-opylidene-beta-D-fructopyranose (6) was straightforwardly transformed into 5-azido-3-O-benzoyl-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose (8), after treatment under modified Garegg's conditions followed by reaction of the resulting 3-O-benzoyl-4-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose (7) with lithium azide in DMF O-debenzoylation at C(3) in 8, followed by oxidation and reduction caused the inversion of the configuration to afford the corresponding beta-D-psicopyranose derivative 11 that was transformed into the related 3,4-di-O-benzyl derivative 12. Cleavage of the acetonide of 12 to give 13 followed by O-tert-butyldiphenylsilylation afforded a resolvable mixture of 14 and 15. Compound 14 was transformed into (2R,3R,4S,5R)- (17) and (2R,3R,4S,5S)-3,4-dibenzyloxy-2',5'-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (18) either by a tandem Staudinger/intramolecular aza-Wittig process and reduction of the resulting intermediate 2 only into 18 by a high stereoselective catalytic hydrogenation. When 15 was subjected to the same protocol, (2S,3S,4R,5R)- (21) and (2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (22) were obtained, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.09.043

文献信息

• Polyhydroxylated pyrrolidines, III. Synthesis of new protected 2,5-dideoxy-2,5-iminohexitols from d-fructose
  作者：Isidoro Izquierdo、María T. Plaza、Miguel Rodríguez、Francisco Franco、Alicia Martos

  DOI：10.1016/j.tet.2005.09.043

  日期：2005.12

  The readily available 3-O-benzoyl-4-O-benzyl-1,2-Oisopi-opylidene-beta-D-fructopyranose (6) was straightforwardly transformed into 5-azido-3-O-benzoyl-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose (8), after treatment under modified Garegg's conditions followed by reaction of the resulting 3-O-benzoyl-4-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose (7) with lithium azide in DMF O-debenzoylation at C(3) in 8, followed by oxidation and reduction caused the inversion of the configuration to afford the corresponding beta-D-psicopyranose derivative 11 that was transformed into the related 3,4-di-O-benzyl derivative 12. Cleavage of the acetonide of 12 to give 13 followed by O-tert-butyldiphenylsilylation afforded a resolvable mixture of 14 and 15. Compound 14 was transformed into (2R,3R,4S,5R)- (17) and (2R,3R,4S,5S)-3,4-dibenzyloxy-2',5'-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (18) either by a tandem Staudinger/intramolecular aza-Wittig process and reduction of the resulting intermediate 2 only into 18 by a high stereoselective catalytic hydrogenation. When 15 was subjected to the same protocol, (2S,3S,4R,5R)- (21) and (2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (22) were obtained, respectively. (c) 2005 Elsevier Ltd. All rights reserved.