4,5:7,8-Di-O-isopropylidene-2-O-methyl-3-deoxy-α-D-manno-2-octulopyranosonic Acid | 130703-03-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,5:7,8-Di-O-isopropylidene-2-O-methyl-3-deoxy-α-D-manno-2-octulopyranosonic Acid
• 英文别名: methyl 3-deoxy-4,5:7,8-di-O-isopropylidene-α-D-manno-2-octulopyranosidonic acid；(3aR,4R,6R,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-methoxy-2,2-dimethyl-3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6-carboxylic acid
• CAS: 130703-03-6
• 化学式: C₁₅H₂₄O₈
• 分子量: 332.351
• InChiKey: IFGOPWXMHXNABV-WPMOFKQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4,5:7,8-Di-O-isopropylidene-2-O-methyl-3-deoxy-α-D-manno-2-octulopyranosonic Acid 在 溶剂黄146 作用下， 反应 0.5h， 生成 3-deoxy-α-D-manno-oct-2-ulosonic acid
  参考文献：
  名称：

  Chemistry of the enolates of 2-acetylthiazole: aldol reactions with chiral aldehydes to give 3-deoxy aldos-2-uloses and 3-deoxy 2-ulosonic acids. A short total synthesis of 3-deoxy-D-manno-2-octulosonic acid (KDO)

  摘要：

  The acetyl group of 2-acetylthiazole (2-ATT) was selectively metalated by treatment with lithium tert-butoxide (the lithium enolate was formed) or triethylamine/zinc chloride/trimethylsilyl chloride (the silyl enol ether was formed). The use of strong bases (LDA, TMP) resulted in substantial deprotonation of the thiazole ring. The lithium enolate of 2-ATT, formed under conditions of kinetic control, reacted with aliphatic and aromatic aldehydes to give the corresponding aldols (beta-hydroxyalkyl 2-thiazolyl ketones) in isolated yields of 51-65%. The reaction of the lithium enolate with chiral compounds, i.e., various alkoxy-substituted aldehydes and one amino aldehyde derivative, occurred with a high degree of anti diastereoselectivity (80-92%), an outcome that was in accord with the Felkin-Ahn model for asymmetric induction. Hemiketalization of the aldols that resulted from the reaction of the enolate with D-glyceraldehyde acetonide and 2-O-benzyl D-erythrose acetonide and subsequent liberation of the formyl group by hydrolytic cleavage of the thiazole ring afforded the corresponding aldosuloses. Oxidation converted these to ulosonic acids. The application of this three-carbon-chain elongation to D-arabinose diacetonide afforded the octulosonic acid KDO in 6.8% overall yield.

  DOI：

  10.1021/jo00018a017
• 作为产物：
  描述：

  2,6-anhydro-1,3-dideoxy-4,5:7,8-di-O-isopropylidene-D-manno-oct-1-enitol 在 sodium chlorite 、 sodium dihydrogenphosphate 、 草酰氯 、 potassium tert-butylate 、 双氧水 、 碘 、 sodium methylate 作用下， 以 甲醇 、 六甲基磷酰三胺 为溶剂， 反应 13.58h， 生成 4,5:7,8-Di-O-isopropylidene-2-O-methyl-3-deoxy-α-D-manno-2-octulopyranosonic Acid
  参考文献：
  名称：

  Cyclization of hydroxy enol ethers: a stereocontrolled approach to 3-deoxy-D-manno-2-octulosonic acid containing disaccharides

  摘要：

  A method for the preparation of the carboxylic acids 14 and 15 has been developed, starting from known 2,3,5,6-di-O-isopropylidene-D-mannofuranose. Esterification of 14 and 15 with methanol, methyl 2,3,4-tri-O-benzyl-alpha-D-glucopyranoside, and 1,2,5,6-di-O-isopropylidene-alpha-D-glucofuranose, followed by reaction with Tebbe reagent and selective deprotection gave, respectively, the key complex hydroxy enol ethers 20, 26, and 35. Stereoselective iodocyclization, followed by transformation of the CH2I appendage into a methyloxycarbonyl group, gave the corresponding protected KDO-containing disaccharides.

  DOI：

  10.1021/jo00041a017

文献信息

• Synthesis of KDO and analogues from a novel mannose-derived precursor
  作者：Govindaraj Kumaran、David R Mootoo

  DOI：10.1016/s0040-4039(01)00615-3

  日期：2001.6

  The application of the readily available 1-thio-1,2-O-isopropylidene acetal (TIA) 6 (four steps from d-mannose) to the synthesis of analogues of KDO is illustrated by the preparation of KDO 1, 1-deoxy-β-KDO 2 and the β-C-KDO glycoside 3.

  的应用程序的容易获得的1-硫代-1,2- Ö异亚丙基缩醛（TIA）6（从d甘露糖四步）至KDO的类似物的合成是通过KDO的制备说明1，1-脱氧β-KDO 2和β-C-KDO糖苷3。
• A concise new route to 3-deoxy-d-manno-2-octulosonic acid (KDO) from D-arabinose and 2-acetylthiazole
  作者：Alessandro Dondoni、Giancarlo Fentin、Marco Fogagnolo、Pedro Merino

  DOI：10.1016/s0040-4039(00)97663-9

  日期：1990.1
• Unexpected Anomeric Selectivity of a 1-<i>C</i>-Arylglycal Donor in Kdo Glycoside Synthesis
  作者：Yuxin Qian、Jianhao Feng、Masood Parvez、Chang-Chun Ling

  DOI：10.1021/jo201531j

  日期：2012.1.6

  A novel class of 1-C-arylglycals was developed and subjected to N-iodosuccinimide-mediated glycosylations with alcohols. Unexpectedly, all reactions provided 2-iodo-beta-D-ketopyranosides in high yields and excellent stereoselectivity. After removal of the 2-iodide by radical conditions, the aryl group was smoothly oxidized to provide the corresponding beta-Kdo glycosides. A mechanism for the stereoselective formation of beta-D-ketopyranosides was proposed, which was supported by evidence from X-ray crystallography.
• Chemistry of the enolates of 2-acetylthiazole: aldol reactions with chiral aldehydes to give 3-deoxy aldos-2-uloses and 3-deoxy 2-ulosonic acids. A short total synthesis of 3-deoxy-D-manno-2-octulosonic acid (KDO)
  作者：Alessandro Dondoni、Pedro Merino

  DOI：10.1021/jo00018a017

  日期：1991.8

  The acetyl group of 2-acetylthiazole (2-ATT) was selectively metalated by treatment with lithium tert-butoxide (the lithium enolate was formed) or triethylamine/zinc chloride/trimethylsilyl chloride (the silyl enol ether was formed). The use of strong bases (LDA, TMP) resulted in substantial deprotonation of the thiazole ring. The lithium enolate of 2-ATT, formed under conditions of kinetic control, reacted with aliphatic and aromatic aldehydes to give the corresponding aldols (beta-hydroxyalkyl 2-thiazolyl ketones) in isolated yields of 51-65%. The reaction of the lithium enolate with chiral compounds, i.e., various alkoxy-substituted aldehydes and one amino aldehyde derivative, occurred with a high degree of anti diastereoselectivity (80-92%), an outcome that was in accord with the Felkin-Ahn model for asymmetric induction. Hemiketalization of the aldols that resulted from the reaction of the enolate with D-glyceraldehyde acetonide and 2-O-benzyl D-erythrose acetonide and subsequent liberation of the formyl group by hydrolytic cleavage of the thiazole ring afforded the corresponding aldosuloses. Oxidation converted these to ulosonic acids. The application of this three-carbon-chain elongation to D-arabinose diacetonide afforded the octulosonic acid KDO in 6.8% overall yield.
• Cyclization of hydroxy enol ethers: a stereocontrolled approach to 3-deoxy-D-manno-2-octulosonic acid containing disaccharides
  作者：Arnaud Haudrechy、Pierre Sinay

  DOI：10.1021/jo00041a017

  日期：1992.7

  A method for the preparation of the carboxylic acids 14 and 15 has been developed, starting from known 2,3,5,6-di-O-isopropylidene-D-mannofuranose. Esterification of 14 and 15 with methanol, methyl 2,3,4-tri-O-benzyl-alpha-D-glucopyranoside, and 1,2,5,6-di-O-isopropylidene-alpha-D-glucofuranose, followed by reaction with Tebbe reagent and selective deprotection gave, respectively, the key complex hydroxy enol ethers 20, 26, and 35. Stereoselective iodocyclization, followed by transformation of the CH2I appendage into a methyloxycarbonyl group, gave the corresponding protected KDO-containing disaccharides.