(3R,4R,5R,6R)-4,5:6,7-Di-O-isopropylidene-3,4,5,6,7-pentahydroxy-1-(2-thiazolyl)-1-heptanone | 130703-01-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3R,4R,5R,6R)-4,5:6,7-Di-O-isopropylidene-3,4,5,6,7-pentahydroxy-1-(2-thiazolyl)-1-heptanone
• 英文别名: (3R)-3-[(4R,5R)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-(1,3-thiazol-2-yl)propan-1-one
• CAS: 130703-01-4
• 化学式: C₁₆H₂₃NO₆S
• 分子量: 357.428
• InChiKey: JKZXSHJDXAGYGH-OJAKKHQRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  115
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (3R,4R,5R,6R)-4,5:6,7-Di-O-isopropylidene-3,4,5,6,7-pentahydroxy-1-(2-thiazolyl)-1-heptanone 在 对甲苯磺酸 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  A concise new route to 3-deoxy-d-manno-2-octulosonic acid (KDO) from D-arabinose and 2-acetylthiazole

  摘要：

  DOI：

  10.1016/s0040-4039(00)97663-9
• 作为产物：
  描述：

  2-乙酰基噻唑 、 2,3-二氟-6-硝基苯胺 在 lithium tert-butoxide 作用下， 生成 (3R,4R,5R,6R)-4,5:6,7-Di-O-isopropylidene-3,4,5,6,7-pentahydroxy-1-(2-thiazolyl)-1-heptanone 、 (3S)-3-[(4R,5R)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-(1,3-thiazol-2-yl)propan-1-one
  参考文献：
  名称：

  A concise new route to 3-deoxy-d-manno-2-octulosonic acid (KDO) from D-arabinose and 2-acetylthiazole

  摘要：

  DOI：

  10.1016/s0040-4039(00)97663-9

文献信息

• Direct Aldol Reaction of Pyruvic Derivatives: Catalytic Attempt To Synthesize Ulosonic Acids
  作者：Osama El-Sepelgy、Darius Schwarzer、Piotr Oskwarek、Jacek Mlynarski

  DOI：10.1002/ejoc.201200325

  日期：2012.5

  catalytic asymmetric aldol reaction of pyruvic aldehyde dimethyl acetal and 2-acetylthiazole with sugar aldehydes is demonstrated to be the key step in the synthesis of 3-deoxy-2-ulosonic acids. Efficient and stereoselective pyruvate aldol reactions are catalyzed by metal-based chiral Trost and Shibasaki catalysts. The presented synthetic methodology mimics aldolase-catalyzed reactions by direct activation

  丙酮醛二甲基缩醛和 2-乙酰噻唑与糖醛的催化不对称羟醛反应被证明是合成 3-脱氧-2-ulosonic 酸的关键步骤。金属基手性 Trost 和 Shibasaki 催化剂可催化高效且立体选择性的丙酮酸醛醇反应。所提出的合成方法通过使用金属基手性催化剂直接活化 C3 丙酮酸等价物来模拟醛缩酶催化的反应，合成 2-keto-3-deoxy-D-glucosonic 酸和 3-deoxy-D-甘露糖-2-辛糖酸衍生物。
• Iterative Methodology for the Stereocontrolled Synthesis of Polyol Chains Employing 2-Acetylthiazole as Lactaldehyde Equivalent
  作者：Alessandro Dondoni、Pedro Merino

  DOI：10.1055/s-1993-25967

  日期：——

  The anti-diastereoselective addition (ds 90-92%) of the lithium enolate of 2-acetylthiazole to chiral (poly)alkoxy aldehydes and the stereocontrolled ketone reduction of the resultant aldols using diisobutylaluminum hydride/tetramethylammonium triacetoxyborohydride followed by the aldehyde unmasking from the thiazolering, afford three-carbon higher homologue aldehydes bearing a syn-or anti-1,3-diol unit. The iterative repetition of the sequence provides a route to polyhydroxylated chains having 1,3- and 1,2-diol units. In this methodology 2-acetylthiazole serves as the surrogate of lactaldehyde and its lithium enolate as the equivalent of the α-hydroxypropanal β-anion synthon.

  将 2-乙酰基噻唑的锂烯酸盐与手性（多）烷氧基醛进行反二向选择性加成（ds 90-92%），并使用二异丁基氢化铝/四甲基三乙酰氧基硼氢化铵对生成的醛进行立体控制的酮还原，然后从噻唑化中拆醛、得到含有同或反-1,3-二醇单元的三碳高同族醛。通过迭代重复该序列，可以得到具有 1,3- 和 1,2- 二醇单元的多羟基链。在这种方法中，2-乙酰基噻唑可作为乳醛的替代物，而其锂烯醇则相当于δ-羟基丙醛的δ-阴离子合物。
• 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.