S-[(1S,2S,2'S,3'aS,5R)-2-isopropyl-5,5'-dimethyl-3',3'a-dihydro-2'H-spiro[cyclohexane-1,6'-imidazo[1,5-b]isoxazol]-4'(5'H)-one-2'-yl]-methyl 1-thio-2-deoxy-2-N-acetamido-3,4,6-tri-O-acetyl-β-D-glucopyranoside | 1359096-72-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: S-[(1S,2S,2'S,3'aS,5R)-2-isopropyl-5,5'-dimethyl-3',3'a-dihydro-2'H-spiro[cyclohexane-1,6'-imidazo[1,5-b]isoxazol]-4'(5'H)-one-2'-yl]-methyl 1-thio-2-deoxy-2-N-acetamido-3,4,6-tri-O-acetyl-β-D-glucopyranoside
• CAS: 1359096-72-2
• 化学式: C₃₀H₄₇N₃O₁₀S
• 分子量: 641.783
• InChiKey: NWNZLDGURGTEJM-APYAIEIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.01
• 重原子数：
  44.0
• 可旋转键数：
  9.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  150.01
• 氢给体数：
  1.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  S-[(1S,2S,2'S,3'aS,5R)-2-isopropyl-5,5'-dimethyl-3',3'a-dihydro-2'H-spiro[cyclohexane-1,6'-imidazo[1,5-b]isoxazol]-4'(5'H)-one-2'-yl]-methyl 1-thio-2-deoxy-2-N-acetamido-3,4,6-tri-O-acetyl-β-D-glucopyranoside 在 palladium on carbon 、 氢气 作用下， 以 乙醇 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 48.0h， 以70%的产率得到3-[(3S,5R,6S,9R)-6-isopropyl-1,9-dimethyl-1,4-diazaspiro[4.5]decan-2-one-3-yl]-(2S)-2-hydroxypropyl 1-thio-2-deoxy-2-N-acetamido-3,4,6-tri-O-acetyl-β-D-glucopyranoside
  参考文献：
  名称：

  Cycloaddition of a chiral nitrone to allylic motifs: an access to enantiopure sugar-based amino acids displaying a stable glycosidic bond and to 4(S)-4-hydroxy-l-ornithine

  摘要：

  A (-)-menthone-derived nitrone and various allyl O-, and S-glycosides reacted at 110 degrees C to afford the corresponding cycloadducts in good yields. For an N-acetylated allyl N-glycoside, an N-glycoside-based product was formed in poor yield with loss of the N-acetyl residue, while the major product 4 (60%), in which the sugar moiety was absent, arose from cleavage of the N-glycosidic bond, under the cyclo-addition conditions. The cycloadducts of the O-, and S-glycoside type were ring-opened and subjected to acidic and basic hydrolysis, for removing the chiral auxiliary. This resulted in glycosidic bond cleavage for O-glycosides and loss of material, while an S-glycoside amino acid was isolated in 78% yield, indicating a higher resistance of the S-glycosidic bond. N-O Bond cleavage and hydrolytic treatments applied to 4 afforded 4(S)-4-hydroxy-L-ornithine in high yield. Use of the nitrone derived from (+)-menthone should afford the enantiomer of 4, both precursors of 4-hydroxy arginine derivatives by guanidination. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.12.048
• 作为产物：
  描述：

  allyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-β-D-glucopyranoside 、 (-)-menthone nitrone 以 甲苯 为溶剂， 反应 120.0h， 以83%的产率得到S-[(1S,2S,2'S,3'aS,5R)-2-isopropyl-5,5'-dimethyl-3',3'a-dihydro-2'H-spiro[cyclohexane-1,6'-imidazo[1,5-b]isoxazol]-4'(5'H)-one-2'-yl]-methyl 1-thio-2-deoxy-2-N-acetamido-3,4,6-tri-O-acetyl-β-D-glucopyranoside
  参考文献：
  名称：

  Cycloaddition of a chiral nitrone to allylic motifs: an access to enantiopure sugar-based amino acids displaying a stable glycosidic bond and to 4(S)-4-hydroxy-l-ornithine

  摘要：

  A (-)-menthone-derived nitrone and various allyl O-, and S-glycosides reacted at 110 degrees C to afford the corresponding cycloadducts in good yields. For an N-acetylated allyl N-glycoside, an N-glycoside-based product was formed in poor yield with loss of the N-acetyl residue, while the major product 4 (60%), in which the sugar moiety was absent, arose from cleavage of the N-glycosidic bond, under the cyclo-addition conditions. The cycloadducts of the O-, and S-glycoside type were ring-opened and subjected to acidic and basic hydrolysis, for removing the chiral auxiliary. This resulted in glycosidic bond cleavage for O-glycosides and loss of material, while an S-glycoside amino acid was isolated in 78% yield, indicating a higher resistance of the S-glycosidic bond. N-O Bond cleavage and hydrolytic treatments applied to 4 afforded 4(S)-4-hydroxy-L-ornithine in high yield. Use of the nitrone derived from (+)-menthone should afford the enantiomer of 4, both precursors of 4-hydroxy arginine derivatives by guanidination. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.12.048