2-methylallyl N-(tert-butyloxycarbonyl)-(S)-phenylalanylglycinate | 219674-28-9

• 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: 2-methylallyl N-(tert-butyloxycarbonyl)-(S)-phenylalanylglycinate
• 英文别名: 2-methylprop-2-enyl 2-[[(2S)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-3-phenylpropanoyl]amino]acetate
• CAS: 219674-28-9
• 化学式: C₂₀H₂₈N₂O₅
• 分子量: 376.453
• InChiKey: BCGGFFFWJNWKCQ-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  93.7
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-methylallyl N-(tert-butyloxycarbonyl)-(S)-phenylalanylglycinate 在 四(三苯基膦)钯 zinc(II) chloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 [N-(tert-butyloxycarbonyl)phenylalanyl]-4,5-didehydroleucine
  参考文献：
  名称：

  Introduction of Allylic Side Chains onto Peptides by Pd(0)-Catalyzed "Ester Enolate Claisen Rearrangement"

  摘要：

  Allylic esters of peptides undergo an ester enolate Claisen rearrangement upon treatment with LDA in the presence of various metal salts (see Table 1). Best results are obtained using zinc chloride. In the presence of a catalytic amount of Pd(0) the rearrangement products are formed in high yields. Addition of Pd(II) has no significant influence on the yield and stereoselectivity of the reaction. In contrast to the rearrangement without Pd(0) the catalyzed reaction probably proceeds; via intermolecular allylic alkylation as is shown in a cross experiment of different allylic esters. The methodology is not limited to dipeptides, but can also be applied to larger peptides as is illustrated in the rearrangement of tripeptide 11. No epimerization of chiral centers is observed under the reaction conditions used.

  DOI：

  10.1021/jo00101a026
• 作为产物：
  描述：

  N-{[(2-甲基-2-丙基)氧基]羰基}苯丙氨酰甘氨酸 、 2-甲基-2-丙烯-1-醇 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 以95%的产率得到2-methylallyl N-(tert-butyloxycarbonyl)-(S)-phenylalanylglycinate
  参考文献：
  名称：

  锰烯醇盐螯合物克莱森重排对肽的修饰

  摘要：

  在金属盐存在下在-70°C下使肽的烯丙基酯去质子化，导致形成金属肽烯醇化物络合物，该化合物在升温至室温后进行克莱森重排，产生立体选择性修饰的肽。到目前为止，用烯醇锰盐可获得最佳结果。对于这些烯醇化物，掺入肽链中的氨基酸对重排无明显影响，对产量和立体化学结果均无影响。因此，该方案非常适合通过使用手性烯丙基醇的酯对肽进行立体选择性修饰。α-烷基化氨基酸也可以掺入肽中。

  DOI：

  10.1002/1099-0690(200004)2000:7<1241::aid-ejoc1241>3.0.co;2-u

文献信息

• Application of the chelate enolate Claisen rearrangement to the modification of dipeptides
  作者：Uli Kazmaier、Sabine Maier

  DOI：10.1039/a805784b

  日期：——

  Manganese enolates of allylic esters of dipeptides are suitable to undergo Claisen rearrangements, giving rise to unsaturated peptides in excellent yield.

  二肽烯丙基酯的锰烯醇化物适合进行克莱森重排，从而产生不饱和肽，且产量极高。
• Modifications of Peptides by Chelate Claisen Rearrangements of Manganese Enolates
  作者：Sabine Maier、Uli Kazmaier

  DOI：10.1002/1099-0690(200004)2000:7<1241::aid-ejoc1241>3.0.co;2-u

  日期：2000.4

  Deprotonation of allylic esters of peptides at -70 °C in the presence of metal salts results in the formation of metal peptide enolate complexes, which undergo Claisen rearrangement on warming to room temperature to produce stereoselectively modified peptides. By far the best results are obtained with manganese enolates. With these enolates, the amino acids incorporated in the peptide chain have no

  在金属盐存在下在-70°C下使肽的烯丙基酯去质子化，导致形成金属肽烯醇化物络合物，该化合物在升温至室温后进行克莱森重排，产生立体选择性修饰的肽。到目前为止，用烯醇锰盐可获得最佳结果。对于这些烯醇化物，掺入肽链中的氨基酸对重排无明显影响，对产量和立体化学结果均无影响。因此，该方案非常适合通过使用手性烯丙基醇的酯对肽进行立体选择性修饰。α-烷基化氨基酸也可以掺入肽中。
• Introduction of Allylic Side Chains onto Peptides by Pd(0)-Catalyzed "Ester Enolate Claisen Rearrangement"
  作者：Uli Kazmaier

  DOI：10.1021/jo00101a026

  日期：1994.11

  Allylic esters of peptides undergo an ester enolate Claisen rearrangement upon treatment with LDA in the presence of various metal salts (see Table 1). Best results are obtained using zinc chloride. In the presence of a catalytic amount of Pd(0) the rearrangement products are formed in high yields. Addition of Pd(II) has no significant influence on the yield and stereoselectivity of the reaction. In contrast to the rearrangement without Pd(0) the catalyzed reaction probably proceeds; via intermolecular allylic alkylation as is shown in a cross experiment of different allylic esters. The methodology is not limited to dipeptides, but can also be applied to larger peptides as is illustrated in the rearrangement of tripeptide 11. No epimerization of chiral centers is observed under the reaction conditions used.