(3S,5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-3-(3'-butenyl)-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one | 135560-74-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (3S,5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-3-(3'-butenyl)-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one
• 英文别名: (3R,5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-3-(3'-butenyl)-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one；benzyl (3R,5R,6S)-3-but-3-enyl-2-oxo-5,6-diphenylmorpholine-4-carboxylate
• CAS: 135560-74-6
• 化学式: C₂₈H₂₇NO₄
• 分子量: 441.527
• InChiKey: XUBJFRWIBHRTJB-CYXNTTPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.0
• 重原子数：
  33.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  55.84
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (3S,5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-3-(3'-butenyl)-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one 在 双(三甲基硅烷基)氨基钾 、 臭氧 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 0.91h， 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
• 作为产物：
  描述：

  4-碘-1-丁烯 、 (2S,3R)-N-苄氧羰基-2,3-二苯基吗啉-6-酮 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 0.17h， 以46.5%的产率得到(3S,5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-3-(3'-butenyl)-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one
  参考文献：
  名称：

  Asymmetric synthesis of monosubstituted and .alpha.,.alpha.-disubstituted .alpha.-amino acids via diastereoselective glycine enolate alkylations

  摘要：

  The enolates derived from the optically active (5S,6R)- and (5R,6S)-4(tert-butyloxycarbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-one (1a,b) and (5S,6R)- and (5R,6S)-4-(benzyloxycarbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-4H-1,4-oxazin-2-ones (2a,b) efficiently couple with alkyl halides to afford the corresponding anti-alpha-monosubstituted oxazinones (3 and 4). The enolate alkylation of the alpha-monosubstituted oxazinones (3 and 4) provides the corresponding alpha,alpha-disubstituted oxazinones (7 and 8). Dissolving-metal reduction of the homologated oxazinones allows the direct preparation of t-BOC-protected alpha-amino acids. In the case of a dissolving-metal-reducible functionality, hydrogenation over a Pd0 catalyst furnishes the zwitterionic amino acids. By employing this protocol several amino acids or their corresponding N-t-BOC derivatives, such as allylglycine, alanine, phenylalanine, beta-ethylaspartic acid, alpha-methylphenylalanine, N-(tert-butyloxycarbonyl)dimethallylglycine, N-(tert-butyloxycarbonyl)-2-(2'-propenyl)norvaline, N-(tert-butyloxycarbonyl)-2-(3'-methyl-2'-butenyl)alanine, N-(tert-butyloxycarbonyl)-2-(2'-propenyl)alanine, 2-(3'-phenylpropyl)alanine, 2-amino-6-(acetyloxy)hexanoic acid, and 2(tert-butyloxycarbonyl)amino-6-[(p-methoxybenzyl)thio]hexanoic acid, are prepared in high enantiomeric excess.

  DOI：

  10.1021/ja00024a038

文献信息

• Asymmetric synthesis of 2,6-diaminopimelic acids
  作者：Robert M. Williams、Chenguang Yuan

  DOI：10.1021/jo00050a028

  日期：1992.11

  The preparations of (RR)-2,6-diaminopimelic acid, (S,S)-2,6-diaminopimelic acid, (SR)-2,6-diaminopimelic acid, and (SS)-2,7-diaminosuberic acid are described. The synthesis of mono-N-protected (SR)-2,6-diaminopimelic acid is also described.