Benzyl 2(S)-<(tert-butoxycarbonyl)amino>hexa-4,5-dienoate | 141362-48-3

• 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: Benzyl 2(S)-<(tert-butoxycarbonyl)amino>hexa-4,5-dienoate
• CAS: 141362-48-3
• 化学式: C₁₈H₂₃NO₄
• 分子量: 317.385
• InChiKey: PHMHVWFLDXBSRX-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  对甲苯磺酸丙炔酯 、 N-BOC-3-碘-L-丙氨酸苄酯 生成 Benzyl 2(S)-<(tert-butoxycarbonyl)amino>hexa-4,5-dienoate
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure Unsaturated .alpha.-Amino Acids Using Serine-Derived Zinc/Copper Reagents

  摘要：

  Treatment of the serine-derived organozinc reagent 2, in benzene/dimethylacetamide, with a THF solution of CuCN . 2LiCl gives rise to a zinc/copper reagent 6 which reacts directly with allylic halides and tosylates to give the corresponding enantiomerically pure substitution products 9 in 32-65% yield (11 examples). The reaction proceeds by formal S(N)2' displacement of the leaving group. Reaction with propargyl halides gives the corresponding terminal allene 12a. The zinc reagent 2 may also be prepared directly from protected iodoalanine 1 in THP by the Knochel method. Reaction with propargylic tosylates as electrophiles gives rise to the corresponding protected terminal allenic amino acids in 51-81% yield (four examples); use of enantiomerically enriched propargylic tosylates results in the formation of diastereoisomerically enriched allenic products. Reactions of the zinc/copper reagent 6 with a range of representative electrophiles is explored; use of relatively reactive electrophiles is necessary to obtain satisfactory yields. Finally, the possibility of using the serine-derived iodide 20, in which the carboxylic acid is protected as a methyl ester, is established: This reagent offers advantages over the corresponding benzyl ester protected reagent 6 for the synthesis of unsaturated amino acids.

  DOI：

  10.1021/jo00112a048

文献信息

• Preparation of enantiomerically pure protected unsaturated α-amino acids from a new serine derived zinc–copper reagent
  作者：Michael J. Dunn、Richard F. W. Jackson

  DOI：10.1039/c39920000319

  日期：——

  Treatment of the iodoalanine derived zinc reagent 1 with Knochel's soluble copper salt (CuCN·2LiCl) allows the preparation of a reactive copper reagent 2 which couples in moderate to good yield with allyl halides to give protected unsaturated α-amino acids in a single step from easily available precursors.

  利用碘丙氨酸衍生的锌试剂1与Knochel可溶性铜盐（CuCN·2LiCl）处理，可制备出一种活性铜试剂2，该试剂与烯丙基卤化物在温和至良好的产率下偶联，可从易获得的起始物直接一步合成得到保护的不饱和α-氨基酸。