(3R,4S)-N-(tert-Butoxycarbonyl)-4,5-N,O-isopropyliden-4-amino-3,5-dihydroxy-1-(2-thiazolyl)-1-pentanone | 128459-42-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: (3R,4S)-N-(tert-Butoxycarbonyl)-4,5-N,O-isopropyliden-4-amino-3,5-dihydroxy-1-(2-thiazolyl)-1-pentanone
• 英文别名: tert-butyl (4S)-4-[(1R)-1-hydroxy-3-oxo-3-(1,3-thiazol-2-yl)propyl]-2,2-dimethyl-1,3-oxazolidine-3-carboxylate
• CAS: 128459-42-7
• 化学式: C₁₆H₂₄N₂O₅S
• 分子量: 356.443
• InChiKey: PTKNTDRKVHNMRC-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.45
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  88.96
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (3R,4S)-N-(tert-Butoxycarbonyl)-4,5-N,O-isopropyliden-4-amino-3,5-dihydroxy-1-(2-thiazolyl)-1-pentanone 在 溶剂黄146 作用下， 以 乙腈 为溶剂， 反应 36.0h， 以94%的产率得到(S)-4-((1R,3R)-1,3-Dihydroxy-3-thiazol-2-yl-propyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  通过噻唑中间体完全化学合成氮杂糖。从丝氨酸到（-）-诺吉霉素，（-）-甘露吉姆霉素及其3-脱氧衍生物的立体发散途径

  摘要：

  （ - ） -的天然产物的对映体野尻霉素（+） -的合成1和mannojirimycin（+） - 2已经由立体控制还原噻唑酮的情况下进行7作为公共关键中间体。该酮又通过涉及羰基烯烃化和二羟基化过程的两种收敛途径从L-丝氨酸衍生的醛3获得。此外，已经由3和2-乙酰基噻唑的烯醇锂制备了（-）- 1和（-）- 2的3-脱氧衍生物，随后立体控制还原了所得的羟醛。

  DOI：

  10.1016/s0040-4020(01)80389-6
• 作为产物：
  描述：

  2-乙酰基噻唑 、 3-反-溴碳-2,2'-二甲基氧酸酯 在 lithium tert-butoxide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以65%的产率得到(3R,4S)-N-(tert-Butoxycarbonyl)-4,5-N,O-isopropyliden-4-amino-3,5-dihydroxy-1-(2-thiazolyl)-1-pentanone
  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