(2S,3R)-methyl 3-hydroxy-2-(4-nitrophenylsulfonamido)butanoate | 1260020-06-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2S,3R)-methyl 3-hydroxy-2-(4-nitrophenylsulfonamido)butanoate
• 英文别名: Nosyl-L-Thr-OMe；methyl (2S,3R)-3-hydroxy-2-[(4-nitrophenyl)sulfonylamino]butanoate
• CAS: 1260020-06-1
• 化学式: C₁₁H₁₄N₂O₇S
• 分子量: 318.307
• InChiKey: JJLNRAPNHRJRGV-XCBNKYQSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  147
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2S,3R)-methyl 3-hydroxy-2-(4-nitrophenylsulfonamido)butanoate 在 N-溴代丁二酰亚胺(NBS) 、 D(+)-10-樟脑磺酸 、 potassium carbonate 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 33.0h， 生成 (2R,3S,6R)-methyl 6-bromo-2,7,7-trimethyl-4-((4-nitrophenyl)sulfonyl)-1,4-oxazepane-3-carboxylate
  参考文献：
  名称：

  Stereo- and Regioselective Synthesis of Polysubstituted Chiral 1,4-Oxazepanes

  摘要：

  The number of cyclic molecular scaffolds available to medicinal chemists remains limited, and simple structures such as oxazepanes are still made using multistep procedures, including a number of protection/deprotection steps and purifications. We report herein an expedient and efficient synthesis of chiral polysubstituted oxazepanes. The developed method relies on a regio- and stereoselective 7-endo cyclization through haloetherification. Mechanistic studies using a combination of computations and experiments confirmed the expected role of the asymmetry of the chiral bromonium intermediate on the haloetherification regioselectivity. Computations also suggested that the bromonium intermediate is formed with no transition state; hence, the stereoselectivity is controlled primarily by the conformation of the substrate. Applied to a set of 16 substrates, tetra- and pentasubstituted oxazepanes were prepared with good yields and moderate to excellent regio- and stereoselectivities.

  DOI：

  10.1021/jo3021715
• 作为产物：
  描述：

  L-苏氨酸甲酯盐酸盐 、 对硝基苯磺酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以82%的产率得到(2S,3R)-methyl 3-hydroxy-2-(4-nitrophenylsulfonamido)butanoate
  参考文献：
  名称：

  新型非蛋白氨基酸的合成：N-乙基-α,β-脱氢氨基酸甲酯

  摘要：

  介绍了从丝氨酸、苏氨酸和苯基丝氨酸衍生物合成 N-乙基-N-(4-硝基苯基-磺酰基)-α,β-脱氢氨基酸衍生物的两种途径。一种途径包括在 4-（二甲氨基）吡啶的催化下，将 N-（4-硝基苯磺酰基）-β-羟基氨基酸酯与二碳酸二叔丁酯脱水，然后将 N-（4-硝基苯磺酰基）-α 烷基化，用三乙基氧鎓四氟硼酸盐获得的β-脱氢氨基酸甲酯。第二种策略应用相同的程序，但顺序相反：烷基化，然后脱水。这些方法使得首次获得新的非天然氨基酸成为可能，其中包含 N-乙基和 α,β-脱氢部分。

  DOI：

  10.1002/ejoc.201001302

文献信息

• Synthesis of Novel Nonproteinogenic Amino Acids: N-Ethyl-α,β-dehydroamino Acid Methyl Esters
  作者：Luís S. Monteiro、Joanna Kołomańska、Ana C. Suarez

  DOI：10.1002/ejoc.201001302

  日期：2010.12

  for the synthesis of N-ethyl-N-(4-nitrophenyl-sulfonyl)-α,β-dehydroamino acid derivatives from serine, threonine and phenylserine derivatives are presented. One route consists of dehydration of N-(4-nitrophenylsulfonyl)-β-hydroxyamino acid esters with di-tert-butyl dicarbonate catalyzed by 4-(dimethylamino)pyridine, followed by alkylation of the N-(4-nitrophenylsulfonyl)-α,β-dehydroamino acid methyl

  介绍了从丝氨酸、苏氨酸和苯基丝氨酸衍生物合成 N-乙基-N-(4-硝基苯基-磺酰基)-α,β-脱氢氨基酸衍生物的两种途径。一种途径包括在 4-（二甲氨基）吡啶的催化下，将 N-（4-硝基苯磺酰基）-β-羟基氨基酸酯与二碳酸二叔丁酯脱水，然后将 N-（4-硝基苯磺酰基）-α 烷基化，用三乙基氧鎓四氟硼酸盐获得的β-脱氢氨基酸甲酯。第二种策略应用相同的程序，但顺序相反：烷基化，然后脱水。这些方法使得首次获得新的非天然氨基酸成为可能，其中包含 N-乙基和 α,β-脱氢部分。
• Stereo- and Regioselective Synthesis of Polysubstituted Chiral 1,4-Oxazepanes
  作者：Michelle Bezanson、Joshua Pottel、Rana Bilbeisi、Sylvestre Toumieux、Mickaël Cueto、Nicolas Moitessier

  DOI：10.1021/jo3021715

  日期：2013.2.1

  The number of cyclic molecular scaffolds available to medicinal chemists remains limited, and simple structures such as oxazepanes are still made using multistep procedures, including a number of protection/deprotection steps and purifications. We report herein an expedient and efficient synthesis of chiral polysubstituted oxazepanes. The developed method relies on a regio- and stereoselective 7-endo cyclization through haloetherification. Mechanistic studies using a combination of computations and experiments confirmed the expected role of the asymmetry of the chiral bromonium intermediate on the haloetherification regioselectivity. Computations also suggested that the bromonium intermediate is formed with no transition state; hence, the stereoselectivity is controlled primarily by the conformation of the substrate. Applied to a set of 16 substrates, tetra- and pentasubstituted oxazepanes were prepared with good yields and moderate to excellent regio- and stereoselectivities.