(Z)-Methyl 2-(formylamino)-4-methyl-2-pentenoate | 72054-64-9

• 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: (Z)-Methyl 2-(formylamino)-4-methyl-2-pentenoate
• 英文别名: 2-formamido-4-methyl-pent-2-enoic acid methyl ester；Z-Methyl-α-formamid-β-isopropylacrylat；methyl (Z)-2-formamido-4-methylpent-2-enoate
• CAS: 72054-64-9
• 化学式: C₈H₁₃NO₃
• 分子量: 171.196
• InChiKey: ZVIGSIJDHSSKSO-DAXSKMNVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-Methyl 2-(formylamino)-4-methyl-2-pentenoate 在 N-溴代丁二酰亚胺(NBS) 、 三乙胺 、 三氯氧磷 作用下， 以 四氯化碳 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 (Z)-Methyl 3-bromo-2-isocyano-4-methyl-2-pentenoate
  参考文献：
  名称：

  A Novel Synthesis of Methyl 1,5-Disubstituted Imidazole-4-carboxylates Using 3-Bromo-2-isocyanoacrylates (BICA)

  摘要：

  Methyl 1,5-disubstituted imidazole-4-carboxylates 1 were synthesised using methyl 3-substituted 3-bromo-2-isocyanoacrylates 3 (BICA), and the reaction mechanism was elucidated. Reactions of 3, which were prepared by bromination of 3-substituted 2-(formylamino)acrylates 6 followed by dehydration of the formylamino group, with a variety of primary amines gave imidazoles 1 in good overall yields. A mechanistic study suggested a Michael reaction of an amine with 3 followed by p-elimination of hydrogen bromide exclusively afforded (E)-N,3-disubstituted 3-amino-2-isocyanoacrylates 2. Geometric isomerization to (Z)-2 with a base and subsequent cyclization gave imidazoles 1.

  DOI：

  10.1021/jo00104a018
• 作为产物：
  描述：

  N-Formyl-leucin-methylester 在 三乙烯二胺 、 次氯酸叔丁酯 作用下， 以 氯仿 、 甲苯 为溶剂， 生成 (Z)-Methyl 2-(formylamino)-4-methyl-2-pentenoate
  参考文献：
  名称：

  A Novel Synthesis of Methyl 1,5-Disubstituted Imidazole-4-carboxylates Using 3-Bromo-2-isocyanoacrylates (BICA)

  摘要：

  Methyl 1,5-disubstituted imidazole-4-carboxylates 1 were synthesised using methyl 3-substituted 3-bromo-2-isocyanoacrylates 3 (BICA), and the reaction mechanism was elucidated. Reactions of 3, which were prepared by bromination of 3-substituted 2-(formylamino)acrylates 6 followed by dehydration of the formylamino group, with a variety of primary amines gave imidazoles 1 in good overall yields. A mechanistic study suggested a Michael reaction of an amine with 3 followed by p-elimination of hydrogen bromide exclusively afforded (E)-N,3-disubstituted 3-amino-2-isocyanoacrylates 2. Geometric isomerization to (Z)-2 with a base and subsequent cyclization gave imidazoles 1.

  DOI：

  10.1021/jo00104a018

文献信息

• (Z)-selective β-bromination ofN-formyl-α, β-dehydroamino acid esters
  作者：Masaki Yamada、Kazuya Nakao、Toshio Fukui、Ken-ichi Nunami

  DOI：10.1016/0040-4020(96)00209-8

  日期：1996.4

  Stereoselective β-bromination ofN-formyl-α, β-dehydroamino acid esters5 was investigated. A reaction of5 with NBS affordedα-bromo-N-formylimines10 which successively isomerized to giveβ-bromo-N-formyl-α, β-dehydroamino acid esters4. The migration of the double bond of the intermediates10 with bulky substituents at the β-position resulted in highly stereoselective formation of(Z)-4, while that of the

  研究了N-甲酰基-α，β-脱氢氨基酸酯5的立体选择性β-溴化。5与NBS的反应得到α-溴-N-甲酰亚胺10，其连续异构化以得到β-溴-N-甲酰-α，β-脱氢氨基酸酯4。具有在β位的大取代基的中间体10的双键的迁移导致（Z）-4的高度立体选择性的形成，而具有大的取代基的底物的双键的非立体选择性地进行。在使用AM1进行半经验计算的基础上，提出了立体选择性溴化的机理。
• High Enantioselectivity Is Induced by a Single Monodentate Phosphoramidite Ligand in Iridium-Catalyzed Asymmetric Hydrogenation
  作者：Francesca Giacomina、Auke Meetsma、Lavinia Panella、Laurent Lefort、André H. M. de Vries、Johannes G. de Vries

  DOI：10.1002/anie.200603930

  日期：2007.2.19
• A Novel Synthesis of Methyl 1,5-Disubstituted Imidazole-4-carboxylates Using 3-Bromo-2-isocyanoacrylates (BICA)
  作者：Ken-ichi Nunami、Masaki Yamada、Toshio Fukui、Kazuo Matsumoto

  DOI：10.1021/jo00104a018

  日期：1994.12

  Methyl 1,5-disubstituted imidazole-4-carboxylates 1 were synthesised using methyl 3-substituted 3-bromo-2-isocyanoacrylates 3 (BICA), and the reaction mechanism was elucidated. Reactions of 3, which were prepared by bromination of 3-substituted 2-(formylamino)acrylates 6 followed by dehydration of the formylamino group, with a variety of primary amines gave imidazoles 1 in good overall yields. A mechanistic study suggested a Michael reaction of an amine with 3 followed by p-elimination of hydrogen bromide exclusively afforded (E)-N,3-disubstituted 3-amino-2-isocyanoacrylates 2. Geometric isomerization to (Z)-2 with a base and subsequent cyclization gave imidazoles 1.