(2R,3S,4S,5R,6S)-2,3,4,6-Tetra-O-benzyl-1,2,3,4,5,6-hexahydroxy-8-N-phthaloyloctan-8-amine | 140386-73-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: (2R,3S,4S,5R,6S)-2,3,4,6-Tetra-O-benzyl-1,2,3,4,5,6-hexahydroxy-8-N-phthaloyloctan-8-amine
• 英文别名: 2-[(3S,4R,5S,6S,7R)-4,8-dihydroxy-3,5,6,7-tetrakis(phenylmethoxy)octyl]isoindole-1,3-dione
• CAS: 140386-73-8
• 化学式: C₄₄H₄₅NO₈
• 分子量: 715.843
• InChiKey: STPWHFKGJJMDAL-PGRNDEIQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  53
• 可旋转键数：
  20
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  115
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2R,3S,4S,5R,6S)-2,3,4,6-Tetra-O-benzyl-1,2,3,4,5,6-hexahydroxy-8-N-phthaloyloctan-8-amine 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 barium dihydroxide 、 potassium permanganate 、 草酰氯 、 buffer (1.25M KH₂PO₄/0.244M K₂HPO₄) 、 四丁基氟化铵 、 一水合肼 、 二甲基亚砜 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 145.67h， 生成 (1S,6S,7R,8S,8aS)-1,6,7,8-Tetra-O-benzyloctahydroindolizin-5-one
  参考文献：
  名称：

  Stereocontrolled total synthesis of the unnatural enantiomers of castanospermine and 1-epi-castanospermine

  摘要：

  A concise practical synthesis (13 steps, ca. 10-12% overall yield) of the unnatural enantiomer of castanospermine ((-)-1) and its 1-epimer 2 from 2,3,4-tri-O-benzyl-D-xylose (3) is described. Key steps in the synthesis are two organometal aldehyde additions, vinylation of 3 to 4 and allylation of 6a to 11, both of which proceed with a considerably high degree of stereocontrol. The fused ring system is generated from the acyclic amino polyol derivative 16a by two successive S(N)2-type cyclizations. Notably, the annulation of the six-membered ring makes use of tetravalent phosphonium reagents (Appel or Mitsunobu type) which cyclize the amino alcohol 22a/b directly to 23a/b without need for N-deprotection and O-activation manipulations.

  DOI：

  10.1021/jo00037a043
• 作为产物：
  描述：

  2,3,4-tri-O-benzyl-D-xylopyranose 在 盐酸 、 chromium chloride 、 lithium aluminium tetrahydride 、 sodium hydride 、 臭氧 、 N,N-二异丙基乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 209.0h， 生成 (2R,3S,4S,5R,6S)-2,3,4,6-Tetra-O-benzyl-1,2,3,4,5,6-hexahydroxy-8-N-phthaloyloctan-8-amine
  参考文献：
  名称：

  Stereocontrolled total synthesis of the unnatural enantiomers of castanospermine and 1-epi-castanospermine

  摘要：

  A concise practical synthesis (13 steps, ca. 10-12% overall yield) of the unnatural enantiomer of castanospermine ((-)-1) and its 1-epimer 2 from 2,3,4-tri-O-benzyl-D-xylose (3) is described. Key steps in the synthesis are two organometal aldehyde additions, vinylation of 3 to 4 and allylation of 6a to 11, both of which proceed with a considerably high degree of stereocontrol. The fused ring system is generated from the acyclic amino polyol derivative 16a by two successive S(N)2-type cyclizations. Notably, the annulation of the six-membered ring makes use of tetravalent phosphonium reagents (Appel or Mitsunobu type) which cyclize the amino alcohol 22a/b directly to 23a/b without need for N-deprotection and O-activation manipulations.

  DOI：

  10.1021/jo00037a043

文献信息

• Stereocontrolled formation of Polysubstitued tetrahydorfurans by debenzylating cycloetherification
  作者：Henrietta Dehmlow、Johann Mulzer、Carsten Seilz、Achim R Strecker、Andreas Kohlmann

  DOI：10.1016/s0040-4039(00)92514-0

  日期：1992.6

  Benzyl ethers with S(N)2 active sites in gamma-position undergo spontaneous regio- and stereocontrolled tetrahydrofuran cyclization with concomitant debenzylation even under mildly acidic or neutral conditions.
• Stereocontrolled total synthesis of the unnatural enantiomers of castanospermine and 1-epi-castanospermine
  作者：Johann Mulzer、Henrietta Dehmlow、Juergen Buschmann、Peter Luger

  DOI：10.1021/jo00037a043

  日期：1992.5

  A concise practical synthesis (13 steps, ca. 10-12% overall yield) of the unnatural enantiomer of castanospermine ((-)-1) and its 1-epimer 2 from 2,3,4-tri-O-benzyl-D-xylose (3) is described. Key steps in the synthesis are two organometal aldehyde additions, vinylation of 3 to 4 and allylation of 6a to 11, both of which proceed with a considerably high degree of stereocontrol. The fused ring system is generated from the acyclic amino polyol derivative 16a by two successive S(N)2-type cyclizations. Notably, the annulation of the six-membered ring makes use of tetravalent phosphonium reagents (Appel or Mitsunobu type) which cyclize the amino alcohol 22a/b directly to 23a/b without need for N-deprotection and O-activation manipulations.