(2S,3S,4S,5R)-ethyl 2-benzyl-4-[(S)-4-isopropyl-2-oxo-3-oxazolidinylcarbonyl]-3-methyl-5-(4-nitrophenyl)tetrahydrofuran-2-carboxylate | 1443117-52-9

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 呋喃类木脂素
• 英文名称: (2S,3S,4S,5R)-ethyl 2-benzyl-4-[(S)-4-isopropyl-2-oxo-3-oxazolidinylcarbonyl]-3-methyl-5-(4-nitrophenyl)tetrahydrofuran-2-carboxylate
• 英文别名: ethyl (2S,3S,4S,5R)-2-benzyl-3-methyl-5-(4-nitrophenyl)-4-[(4S)-2-oxo-4-propan-2-yl-1,3-oxazolidine-3-carbonyl]oxolane-2-carboxylate
• CAS: 1443117-52-9
• 化学式: C₂₈H₃₂N₂O₈
• 分子量: 524.571
• InChiKey: STWJHRPFYOFEEH-GXBGQURWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  38
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  128
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  苯丙酸,a-重氮基-,乙基酯 、 (S)-3-crotonoyl-4-isopropyl-2-oxazolidinone 、 对硝基苯甲醛 在 rhodium(II) pivalate 、 nickel(II) tetrafluoroborate hexahydrate 作用下， 以 二氯甲烷 为溶剂， 反应 1.17h， 以64%的产率得到(2S,3S,4S,5R)-ethyl 2-benzyl-4-[(S)-4-isopropyl-2-oxo-3-oxazolidinylcarbonyl]-3-methyl-5-(4-nitrophenyl)tetrahydrofuran-2-carboxylate
  参考文献：
  名称：

  Diastereoselective Synthesis of Tetrahydrofurans by Lewis Acid Catalyzed Intermolecular Carbenoid–Carbonyl Reaction–Cycloaddition Sequences: Unusual Diastereoselectivity of Lewis Acid Catalyzed Cycloadditions

  摘要：

  The effects of including metal salts for three. component reactions involving alpha-alkyl-alpha-diazo esters, aromatic aldehydes, and 3-(2-alkenoyl)-2-oxazolidinones are described, in terms of yields and diastereoselectivities. Metal tetrafluorborates (10-30 mol %) such as Co(BF4)(2)center dot 6H(2)O, Ni(BF4)(2)center dot 6H(2)O, and AgBF4 were effective in delivering high yields and diastereoselectivities (93:7 to 99:1) of the corresponding tetrahydrofuran derivatives while suppressing the competitive formation of 1,3-dioxolane. Using (S)-3-(2-alkenoyl)-4-isopropyl-2-oxazolidinones as the dipolarophiles in the three-component reactions, in the presence of Ni(BF4)(2)center dot 6H(2)O or Co(ClO4)(2)center dot 6H(2)O (10-30 mol %), optically active tetrahydrofurans that possess four successive asymmetric centers were synthesized in high diastereoselectivities (99:1). On the basis of the configuration of the cycloadduct using the X-ray analysis, the high diastereoselectivity could be explained by the unusual Re-face approach to the dipolarophile in the presence of the Lewis acid, proceeding through the s-cis conformer of the 3-(2-alkenoyl)-2-oxazolidinone with the two carbonyls in opposing directions (dipole-dipole interaction).

  DOI：

  10.1021/jo400858u

文献信息

• Diastereoselective Synthesis of Tetrahydrofurans by Lewis Acid Catalyzed Intermolecular Carbenoid–Carbonyl Reaction–Cycloaddition Sequences: Unusual Diastereoselectivity of Lewis Acid Catalyzed Cycloadditions
  作者：Yuta Hashimoto、Kennosuke Itoh、Akikazu Kakehi、Motoo Shiro、Hiroyuki Suga

  DOI：10.1021/jo400858u

  日期：2013.6.21

  The effects of including metal salts for three. component reactions involving alpha-alkyl-alpha-diazo esters, aromatic aldehydes, and 3-(2-alkenoyl)-2-oxazolidinones are described, in terms of yields and diastereoselectivities. Metal tetrafluorborates (10-30 mol %) such as Co(BF4)(2)center dot 6H(2)O, Ni(BF4)(2)center dot 6H(2)O, and AgBF4 were effective in delivering high yields and diastereoselectivities (93:7 to 99:1) of the corresponding tetrahydrofuran derivatives while suppressing the competitive formation of 1,3-dioxolane. Using (S)-3-(2-alkenoyl)-4-isopropyl-2-oxazolidinones as the dipolarophiles in the three-component reactions, in the presence of Ni(BF4)(2)center dot 6H(2)O or Co(ClO4)(2)center dot 6H(2)O (10-30 mol %), optically active tetrahydrofurans that possess four successive asymmetric centers were synthesized in high diastereoselectivities (99:1). On the basis of the configuration of the cycloadduct using the X-ray analysis, the high diastereoselectivity could be explained by the unusual Re-face approach to the dipolarophile in the presence of the Lewis acid, proceeding through the s-cis conformer of the 3-(2-alkenoyl)-2-oxazolidinone with the two carbonyls in opposing directions (dipole-dipole interaction).