5-hexenyl 3,4,6-tri-O-benzyl-2-C-formylmethyl-2-deoxy-β-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-hexenyl 3,4,6-tri-O-benzyl-2-C-formylmethyl-2-deoxy-β-D-glucopyranoside
• 英文别名: 2-[(2R,3R,4R,5S,6R)-2-hex-5-enoxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl]acetaldehyde
• 化学式: C₃₅H₄₂O₆
• 分子量: 558.715
• InChiKey: ZDLYBVZMWKKADY-ZQPTVKGJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  41
• 可旋转键数：
  18
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1-(3',4',6'-tri-O-benzyl-α-D-mannopyranosyl)prop-2-ene 在 吡啶 、 potassium carbonate 、 臭氧 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 5-hexenyl 3,4,6-tri-O-benzyl-2-C-formylmethyl-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  1,2-Migration of 2‘-Oxoalkyl Group and Concomitant Synthesis of 2-C-Branched O-, S-Glycosides and Glycosyl Azides via 1,2-Cyclopropanated Sugars

  摘要：

  Treatment of 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-mannosides (4, 5, and 6) with base resulted in 1,2-cyclopropanation via an intramolecular S(N)2 reaction due to their 1,2-trans-diaxial configurations. The 1,2-cyclopropanated sugars (10 and 13) were reacted with various alcohols, thiols, and sodium azide to produce 2-C-branched O- and S-glycosides and glycosyl azides (11, 14-28) in good to excellent yields. In contrast, 1,2-cis 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-glucoside 9 formed an acyclic conjugated aldehyde (31) under basic conditions, which occurred by 1'-enolation followed by beta-elimination. An intramolecular Michael addition from 31 produced 2-O-Ms-beta-C-glucoside 30 as a major product. However, due to the electron-withdrawing effect exerted by 2-O-Ms compound 31 also undergoes a C2 epimerization to form 32. Thereafter, the intramolecular Michael addition led to the formation of both 1,2-trans 2'-oxoalkyl 2-O-Ms-alpha-C-mannoside 4 and its beta-anomer (33). Because beta-elimination/Michael addition and C2 epimerization are reversible reactions, equilibriums among 9, 31, 30, 32, 33, and 4 were established, which included the transformation of 1,2-cis C-glucoside 9 into 1,2-trans C-mannoside 4. The subsequent 1,2-cyclopropanation of 4 was an irreversible reaction yielding 1,2-cyclopropanated 10 and further conversion to 1,2-migration products (11 and 12).

  DOI：

  10.1021/jo0502854

文献信息

• 1,2-Migration of 2‘-Oxoalkyl Group and Concomitant Synthesis of 2-<i>C</i>-Branched <i>O</i>-, <i>S</i>-Glycosides and Glycosyl Azides via 1,2-Cyclopropanated Sugars
  作者：Huawu Shao、Sanchai Ekthawatchai、Chien-Sheng Chen、Shih-Hsiung Wu、Wei Zou

  DOI：10.1021/jo0502854

  日期：2005.6.1

  Treatment of 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-mannosides (4, 5, and 6) with base resulted in 1,2-cyclopropanation via an intramolecular S(N)2 reaction due to their 1,2-trans-diaxial configurations. The 1,2-cyclopropanated sugars (10 and 13) were reacted with various alcohols, thiols, and sodium azide to produce 2-C-branched O- and S-glycosides and glycosyl azides (11, 14-28) in good to excellent yields. In contrast, 1,2-cis 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-glucoside 9 formed an acyclic conjugated aldehyde (31) under basic conditions, which occurred by 1'-enolation followed by beta-elimination. An intramolecular Michael addition from 31 produced 2-O-Ms-beta-C-glucoside 30 as a major product. However, due to the electron-withdrawing effect exerted by 2-O-Ms compound 31 also undergoes a C2 epimerization to form 32. Thereafter, the intramolecular Michael addition led to the formation of both 1,2-trans 2'-oxoalkyl 2-O-Ms-alpha-C-mannoside 4 and its beta-anomer (33). Because beta-elimination/Michael addition and C2 epimerization are reversible reactions, equilibriums among 9, 31, 30, 32, 33, and 4 were established, which included the transformation of 1,2-cis C-glucoside 9 into 1,2-trans C-mannoside 4. The subsequent 1,2-cyclopropanation of 4 was an irreversible reaction yielding 1,2-cyclopropanated 10 and further conversion to 1,2-migration products (11 and 12).