3-(R)-1-(benzyloxy)-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl-5,6-dihydro-1,4-dithiine-2-carbaldehyde | 1219030-98-4

• 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-(R)-1-(benzyloxy)-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl-5,6-dihydro-1,4-dithiine-2-carbaldehyde
• 英文别名: 6-[(R)-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-phenylmethoxymethyl]-2,3-dihydro-1,4-dithiine-5-carbaldehyde
• CAS: 1219030-98-4
• 化学式: C₁₈H₂₂O₄S₂
• 分子量: 366.502
• InChiKey: XABLIHGFCOEIGI-GOEBONIOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  95.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  甲醇 、 3-(R)-1-(benzyloxy)-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl-5,6-dihydro-1,4-dithiine-2-carbaldehyde 在 Amberlyst 15 作用下， 反应 1.17h， 以59.5%的产率得到[(5R,7S,8R)-8-(benzyloxy)-5-methoxy-3,5,7,8-tetrahydro-2H-[1,4]dithiino[2,3-c]pyran-7-yl]methanol
  参考文献：
  名称：

  Highly Stereoselective de Novo Synthesis of l-Hexoses

  摘要：

  An efficient and general de novo synthetic route to enantiomerically pure L-hexoses has been accomplished starting from the heterocyclic homologating agent 5,6-dihydro-1,4-dithiin-2-yl[(4-methoxybentyl)oxy]methane and methyl alpha,beta-isopropylidene-L-glycerate. The sugar scaffold was constructed by an acid-catalyzed domino reaction, which enabled selective preparation of either methyl 2,3-dideoxy-alpha-L-threohex-2-enopyranosides or 1,6-anhydro-2,3-dideoxy-beta-L-threo-hex-2-enopyranose as key intermediates. The subsequent double bond functionalization by syn or anti dihydroxylation reactions allowed introduction of the remaining stereogenic centers, leading to desired orthogonally protected L-hexopyranosides with a high degree of diastereoselectivity and with very good overall yields. These and previous results (based on the use of the corresponding L-erythro epimers) contribute to make our approach general and place it among the few methods able to synthesize the whole series of the rare L-hexoses.

  DOI：

  10.1021/jo100077k
• 作为产物：
  描述：

  (3-(R)-1-(benzyloxy)-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl-5,6-dihydro-1,4-dithiin-2-yl)methanol 在 吡啶 、 pyridinium chlorochromate 作用下， 反应 8.0h， 以95%的产率得到3-(R)-1-(benzyloxy)-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl-5,6-dihydro-1,4-dithiine-2-carbaldehyde
  参考文献：
  名称：

  Highly Stereoselective de Novo Synthesis of l-Hexoses

  摘要：

  An efficient and general de novo synthetic route to enantiomerically pure L-hexoses has been accomplished starting from the heterocyclic homologating agent 5,6-dihydro-1,4-dithiin-2-yl[(4-methoxybentyl)oxy]methane and methyl alpha,beta-isopropylidene-L-glycerate. The sugar scaffold was constructed by an acid-catalyzed domino reaction, which enabled selective preparation of either methyl 2,3-dideoxy-alpha-L-threohex-2-enopyranosides or 1,6-anhydro-2,3-dideoxy-beta-L-threo-hex-2-enopyranose as key intermediates. The subsequent double bond functionalization by syn or anti dihydroxylation reactions allowed introduction of the remaining stereogenic centers, leading to desired orthogonally protected L-hexopyranosides with a high degree of diastereoselectivity and with very good overall yields. These and previous results (based on the use of the corresponding L-erythro epimers) contribute to make our approach general and place it among the few methods able to synthesize the whole series of the rare L-hexoses.

  DOI：

  10.1021/jo100077k

文献信息

• Highly Stereoselective <i>de Novo</i> Synthesis of <scp>l</scp>-Hexoses
  作者：Annalisa Guaragna、Daniele D’Alonzo、Concetta Paolella、Carmela Napolitano、Giovanni Palumbo

  DOI：10.1021/jo100077k

  日期：2010.6.4

  An efficient and general de novo synthetic route to enantiomerically pure L-hexoses has been accomplished starting from the heterocyclic homologating agent 5,6-dihydro-1,4-dithiin-2-yl[(4-methoxybentyl)oxy]methane and methyl alpha,beta-isopropylidene-L-glycerate. The sugar scaffold was constructed by an acid-catalyzed domino reaction, which enabled selective preparation of either methyl 2,3-dideoxy-alpha-L-threohex-2-enopyranosides or 1,6-anhydro-2,3-dideoxy-beta-L-threo-hex-2-enopyranose as key intermediates. The subsequent double bond functionalization by syn or anti dihydroxylation reactions allowed introduction of the remaining stereogenic centers, leading to desired orthogonally protected L-hexopyranosides with a high degree of diastereoselectivity and with very good overall yields. These and previous results (based on the use of the corresponding L-erythro epimers) contribute to make our approach general and place it among the few methods able to synthesize the whole series of the rare L-hexoses.