3-C-(3,6-di-O-benzyl-4-deoxy-α-D-glycero-2-ulopyranosyl)propene | 374900-66-0

• 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-C-(3,6-di-O-benzyl-4-deoxy-α-D-glycero-2-ulopyranosyl)propene
• 英文别名: (2S,6R)-4-phenylmethoxy-2-(phenylmethoxymethyl)-6-prop-2-enyl-2H-pyran-5-one
• CAS: 374900-66-0
• 化学式: C₂₃H₂₄O₄
• 分子量: 364.441
• InChiKey: FVHRJWZROYKMMX-LEWJYISDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-C-(3,6-di-O-benzyl-4-deoxy-α-D-glycero-2-ulopyranosyl)propene 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 72.0h， 生成 (+/-)-c-5-allyl-2-benzyloxy-r-4-benzyloxymethyl-5-hydroxycyclopent-2-enone 、 (+/-)-2-benzyloxy-r-4-benzyloxymethyl-t-5-hydroxy-5-propenylcyclopent-2-enone
  参考文献：
  名称：

  Multifunctionalized α,β-cyclopentenones from C-2 and C-4-ulopyranosyl compounds: a stereospecific rearrangement initiated by base

  摘要：

  Base treatment of O-benzyl protected C-2- or C-4-ulopyranosyl compounds (4 alpha, 4 beta, and 11) by either 10% Et3N or 1% K2CO3 in MeOH initiated a beta elimination to afford alpha,beta-unsaturated C-ulopyranosyl compounds (5 alpha, 5 beta, and 12), which further rearranged in a stereocontrolled manner to multifuctionalized alpha,beta-cyclopentenones (6 and 14) in 70-80% yield. Both C-alpha- and C-beta-2-ulosides (5 alpha and 5 beta) produced the same cyclopentenone 6, indicating that a 1,2-enolate is formed prior to the cleavage of the C-5-O bond. Because 6 is racemic, it was probably formed by the intramolecular cycloaldolization of two equally populated enantiomeric intermediates. When treated with 90% Et3N in MeOH, 5 alpha yielded almost exclusively 15 (isomer of 6), which was formed by a migration of the double bond in 5 alpha during the previously described rearrangement. Thus either 6 or 15 was the major product, depending on the base used. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00187-2
• 作为产物：
  描述：

  3-C-(3,4,6-tri-O-benzyl-α-D-arabino-hex-2-ulopyranosyl)propene 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以93%的产率得到3-C-(3,6-di-O-benzyl-4-deoxy-α-D-glycero-2-ulopyranosyl)propene
  参考文献：
  名称：

  Multifunctionalized α,β-cyclopentenones from C-2 and C-4-ulopyranosyl compounds: a stereospecific rearrangement initiated by base

  摘要：

  Base treatment of O-benzyl protected C-2- or C-4-ulopyranosyl compounds (4 alpha, 4 beta, and 11) by either 10% Et3N or 1% K2CO3 in MeOH initiated a beta elimination to afford alpha,beta-unsaturated C-ulopyranosyl compounds (5 alpha, 5 beta, and 12), which further rearranged in a stereocontrolled manner to multifuctionalized alpha,beta-cyclopentenones (6 and 14) in 70-80% yield. Both C-alpha- and C-beta-2-ulosides (5 alpha and 5 beta) produced the same cyclopentenone 6, indicating that a 1,2-enolate is formed prior to the cleavage of the C-5-O bond. Because 6 is racemic, it was probably formed by the intramolecular cycloaldolization of two equally populated enantiomeric intermediates. When treated with 90% Et3N in MeOH, 5 alpha yielded almost exclusively 15 (isomer of 6), which was formed by a migration of the double bond in 5 alpha during the previously described rearrangement. Thus either 6 or 15 was the major product, depending on the base used. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00187-2