[(2S,3S)-3-((3aS,5aR,8aR,8bS)-2,2,7,7-Tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-3a-yl)-oxiranyl]-methanol | 186378-67-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: [(2S,3S)-3-((3aS,5aR,8aR,8bS)-2,2,7,7-Tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-3a-yl)-oxiranyl]-methanol
• 英文别名: [(2S,3S)-3-[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]oxiran-2-yl]methanol
• CAS: 186378-67-6
• 化学式: C₁₄H₂₂O₇
• 分子量: 302.324
• InChiKey: SPLCXXYWZJCJHV-OURHRXNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  78.9
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(2S,3S)-3-((3aS,5aR,8aR,8bS)-2,2,7,7-Tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-3a-yl)-oxiranyl]-methanol 在 红铝 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 2.0h， 以60%的产率得到(S)-1-((3aS,5aR,8aR,8bS)-2,2,7,7-Tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-3a-yl)-propane-1,3-diol
  参考文献：
  名称：

  A highly diastereoselective synthesis of 4-octulose and 2-deoxy-4-octulose from a d-fructose derivative

  摘要：

  Bishydroxylation of methyl (Z)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-beta-D-arabino-oct-2-ene-4-ulo-4,8-pyranosonate 1 with osmium tetraoxide proceeded with extremed high diastereoselectivity to give only methyl 4,5:6,7-di-O-isopropylidene-beta-D-arabino-L-erythro-oct-4-ulo-4,8-pyranosonate 2. Configurations of the new stereogenic centers (C-2,3) in 2 were determined by degradation of the C-5,6,7,8 fragment to the well-known methyl 2,3,4-tri-O-methyl-D-(+)-erythronate. 7. Transformation of 2 into the required D-arabino-L-erythro-oct-4-ulosa 10, was achieved by a methodology that implied, protection to 8, reduction of the ester group in 8 to a hydroxymethyl group in 9, and finally deprotection to the free D-arabino-L-erythro-oct-4-ulosa 10. On the other hand, epoxidation reaction on (E)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-beta-D-arabino-oct-2-ene-4-ulo-4,8-pyranose 11 afforded only the corresponding 2,3-anhydro derivative 12 with beta-D-arabino-D-threo configuration, as could be demonstrated by degradation to (S)-1,2,4-trimetoxybutane 16, which synthesis is reported herein. Copyright (C) 1996 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(96)00468-5
• 作为产物：
  描述：

  (E)-3-(1,2;3,4-di-O-isopropylidene-β-D-arabinopyranosyl)-2-propenol 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以83.4%的产率得到[(2S,3S)-3-((3aS,5aR,8aR,8bS)-2,2,7,7-Tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-3a-yl)-oxiranyl]-methanol
  参考文献：
  名称：

  A highly diastereoselective synthesis of 4-octulose and 2-deoxy-4-octulose from a d-fructose derivative

  摘要：

  Bishydroxylation of methyl (Z)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-beta-D-arabino-oct-2-ene-4-ulo-4,8-pyranosonate 1 with osmium tetraoxide proceeded with extremed high diastereoselectivity to give only methyl 4,5:6,7-di-O-isopropylidene-beta-D-arabino-L-erythro-oct-4-ulo-4,8-pyranosonate 2. Configurations of the new stereogenic centers (C-2,3) in 2 were determined by degradation of the C-5,6,7,8 fragment to the well-known methyl 2,3,4-tri-O-methyl-D-(+)-erythronate. 7. Transformation of 2 into the required D-arabino-L-erythro-oct-4-ulosa 10, was achieved by a methodology that implied, protection to 8, reduction of the ester group in 8 to a hydroxymethyl group in 9, and finally deprotection to the free D-arabino-L-erythro-oct-4-ulosa 10. On the other hand, epoxidation reaction on (E)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-beta-D-arabino-oct-2-ene-4-ulo-4,8-pyranose 11 afforded only the corresponding 2,3-anhydro derivative 12 with beta-D-arabino-D-threo configuration, as could be demonstrated by degradation to (S)-1,2,4-trimetoxybutane 16, which synthesis is reported herein. Copyright (C) 1996 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(96)00468-5

文献信息

• A highly diastereoselective synthesis of 4-octulose and 2-deoxy-4-octulose from a d-fructose derivative
  作者：Isidoro Izquierdo、María T. Plaza、Rafael Robles、Concepción Rodríguez

  DOI：10.1016/s0957-4166(96)00468-5

  日期：1996.12

  Bishydroxylation of methyl (Z)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-beta-D-arabino-oct-2-ene-4-ulo-4,8-pyranosonate 1 with osmium tetraoxide proceeded with extremed high diastereoselectivity to give only methyl 4,5:6,7-di-O-isopropylidene-beta-D-arabino-L-erythro-oct-4-ulo-4,8-pyranosonate 2. Configurations of the new stereogenic centers (C-2,3) in 2 were determined by degradation of the C-5,6,7,8 fragment to the well-known methyl 2,3,4-tri-O-methyl-D-(+)-erythronate. 7. Transformation of 2 into the required D-arabino-L-erythro-oct-4-ulosa 10, was achieved by a methodology that implied, protection to 8, reduction of the ester group in 8 to a hydroxymethyl group in 9, and finally deprotection to the free D-arabino-L-erythro-oct-4-ulosa 10. On the other hand, epoxidation reaction on (E)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-beta-D-arabino-oct-2-ene-4-ulo-4,8-pyranose 11 afforded only the corresponding 2,3-anhydro derivative 12 with beta-D-arabino-D-threo configuration, as could be demonstrated by degradation to (S)-1,2,4-trimetoxybutane 16, which synthesis is reported herein. Copyright (C) 1996 Elsevier Science Ltd.