(3R,5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-3-(2'-carbonylethyl)-3-(methoxymethyl)-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one | 135560-76-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3R,5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-3-(2'-carbonylethyl)-3-(methoxymethyl)-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one
• 英文别名: benzyl (3R,5R,6S)-3-(methoxymethyl)-2-oxo-3-(3-oxopropyl)-5,6-diphenylmorpholine-4-carboxylate
• CAS: 135560-76-8
• 化学式: C₂₉H₂₉NO₆
• 分子量: 487.552
• InChiKey: CJHRYNGJKZXQRQ-UWPQIUOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.03
• 重原子数：
  36.0
• 可旋转键数：
  9.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  82.14
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (3R,5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-3-(2'-carbonylethyl)-3-(methoxymethyl)-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one 在 三氟甲磺酸二丁硼 、 sodium hexamethyldisilazane 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 benzyl (3R,5R,6S)-3-(methoxymethyl)-2-oxo-3-[(3S)-3-[(3S,5S,6R)-2-oxo-5,6-diphenyl-4-phenylmethoxycarbonylmorpholin-3-yl]-3-phenoxycarbothioyloxypropyl]-5,6-diphenylmorpholine-4-carboxylate
  参考文献：
  名称：

  Asymmetric synthesis of 2,6-diamino-6-(hydroxymethyl)pimelic acid: assignment of stereochemistry

  摘要：

  The asymmetric synthesis of (2S,6R)-2,6-diamino-6-(hydroxymethyl)pimelic acid (17) and (2S,6S)-2,6-diamino-6-(hydroxymethyl)pimelic acid (4) has been accomplished. Sequential enolate alkylation of (5S,6R)-4-(benzyloxy-carbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-1,4-oxazin-2-one (9) with 1-iodo-3-butene and bromomethyl methyl ether gave the alpha,alpha-disubstituted lactone in approximately 100% de; subsequent ozonolysis gave the quaternary aldehyde 19. Aldol condensation with the enol borane of (5S,6R)-4-(benzyloxycarbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-1,4-oxazin-2-one (9) gave the dilactone 20. Barton deoxygenation, reductive cleavage of the oxazinones, and demethylation gave (2S,6S)-2,6-diamino-6-(hydroxy-methyl)pimelic acid (4). Synthesis of the 2S,6R isomer followed the same protocol, only starting with (5R,6S)-4-(benzyl-oxycarbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-1,4-oxazin-2-one (5). Comparison of these two amino acids reveals that the 2S,6S isomer 4 is the constituent of natural N-[2,6-diamino-6-(hydroxymethyl)pimel-1-yl]-L-alanine (3), a natural antibiotic produced by Micromonospora chalcea.

  DOI：

  10.1021/ja00018a040
• 作为产物：
  描述：

  (2S,3R)-N-苄氧羰基-2,3-二苯基吗啉-6-酮 在 六甲基磷酰三胺 、 双(三甲基硅烷基)氨基钾 、 臭氧 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 2.08h， 生成 (3R,5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-3-(2'-carbonylethyl)-3-(methoxymethyl)-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one
  参考文献：
  名称：

  Asymmetric synthesis of 2,6-diamino-6-(hydroxymethyl)pimelic acid: assignment of stereochemistry

  摘要：

  The asymmetric synthesis of (2S,6R)-2,6-diamino-6-(hydroxymethyl)pimelic acid (17) and (2S,6S)-2,6-diamino-6-(hydroxymethyl)pimelic acid (4) has been accomplished. Sequential enolate alkylation of (5S,6R)-4-(benzyloxy-carbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-1,4-oxazin-2-one (9) with 1-iodo-3-butene and bromomethyl methyl ether gave the alpha,alpha-disubstituted lactone in approximately 100% de; subsequent ozonolysis gave the quaternary aldehyde 19. Aldol condensation with the enol borane of (5S,6R)-4-(benzyloxycarbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-1,4-oxazin-2-one (9) gave the dilactone 20. Barton deoxygenation, reductive cleavage of the oxazinones, and demethylation gave (2S,6S)-2,6-diamino-6-(hydroxy-methyl)pimelic acid (4). Synthesis of the 2S,6R isomer followed the same protocol, only starting with (5R,6S)-4-(benzyl-oxycarbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-1,4-oxazin-2-one (5). Comparison of these two amino acids reveals that the 2S,6S isomer 4 is the constituent of natural N-[2,6-diamino-6-(hydroxymethyl)pimel-1-yl]-L-alanine (3), a natural antibiotic produced by Micromonospora chalcea.

  DOI：

  10.1021/ja00018a040