2-C-(3,4,6-tri-O-benzyl-2-O-mesyl-α-D-mannopyranosyl)acetaldehyde | 857419-63-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-C-(3,4,6-tri-O-benzyl-2-O-mesyl-α-D-mannopyranosyl)acetaldehyde
• 英文别名: [(2R,3R,4S,5R,6R)-2-(2-oxoethyl)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl] methanesulfonate
• CAS: 857419-63-7
• 化学式: C₃₀H₃₄O₈S
• 分子量: 554.661
• InChiKey: CIVUPZHTCKUIIA-WYQCABFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  39
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  106
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-C-(3,4,6-tri-O-benzyl-2-O-mesyl-α-D-mannopyranosyl)acetaldehyde 在 sodium azide 、 三乙胺 作用下， 以 甲醇 为溶剂， 生成 ((2R,3R,4R,5S,6R)-2-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl)-acetaldehyde
  参考文献：
  名称：

  来自2'-羰基烷基2-O-Ms（Ts）-C-糖苷的2-C分支糖苷。通过1,2-环丙烷化的糖进行的串联SN2-SN2反应。

  摘要：

  [反应：请参见文本]在基本条件下，2'-醛基（丙酮基）2-O-Ms（Ts）-α-C-糖苷会经历分子内S（N）2反应形成1,2-环丙烷化糖，在异头碳处与亲核试剂（醇，硫醇和叠氮化物）反应，生成2 C支链糖苷。相比之下，衍生自2'-酮的1,2-环丙烷仅与硫醇反应生成2-C-支链硫代糖苷。

  DOI：

  10.1021/ol0486627
• 作为产物：
  描述：

  1-(3',4',6'-tri-O-benzyl-α-D-mannopyranosyl)prop-2-ene 在 臭氧 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 2-C-(3,4,6-tri-O-benzyl-2-O-mesyl-α-D-mannopyranosyl)acetaldehyde
  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

• 2-C<i>-</i>Branched Glycosides from 2‘-Carbonylalkyl 2-<i>O-</i>Ms(Ts)-<i>C-</i>Glycosides. A Tandem S_N2−S_N2 Reaction via 1,2-Cyclopropanated Sugars
  作者：Huawu Shao、Sanchai Ekthawatchai、Shih-Hsiung Wu、Wei Zou

  DOI：10.1021/ol0486627

  日期：2004.9.1

  [reaction: see text] Under basic conditions, 2'-aldehydo (acetonyl) 2-O-Ms(Ts)-alpha-C-glycosides undergo an intramolecular S(N)2 reaction to form 1,2-cyclopropanated sugars, which react with nucleophiles (alcohols, thiols, and azide) at the anomeric carbon to give 2-C-branched glycosides. By way of contrast, the 1,2-cyclopropanes derived from 2'-ketones only react with thiols to give 2-C-branched

  [反应：请参见文本]在基本条件下，2'-醛基（丙酮基）2-O-Ms（Ts）-α-C-糖苷会经历分子内S（N）2反应形成1,2-环丙烷化糖，在异头碳处与亲核试剂（醇，硫醇和叠氮化物）反应，生成2 C支链糖苷。相比之下，衍生自2'-酮的1,2-环丙烷仅与硫醇反应生成2-C-支链硫代糖苷。
• 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).