Methyl 2-<(allyloxycarbonyl)amino>-2-methoxyacetate | 106928-47-6

• 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: Methyl 2-<(allyloxycarbonyl)amino>-2-methoxyacetate
• 英文别名: N-(methoxycarbonyl)-DL-allylglycine methyl ester；methyl (2RS)-2-[N-(methyloxycarbonyl)amino]pent-4-enoate；methyl 2-((methoxycarbonyl)amino)pent-4-enoate；Methyl N-methoxycarbonyl-2-amino-4-pentenoate；methyl 2-(methoxycarbonylamino)pent-4-enoate
• CAS: 106928-47-6
• 化学式: C₈H₁₃NO₄
• 分子量: 187.196
• InChiKey: ZRVJASUWHAAIIM-UHFFFAOYSA-N

物化性质

• 沸点：
  262.9±33.0 °C(Predicted)
• 密度：
  1.089±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 2-<(allyloxycarbonyl)amino>-2-methoxyacetate 在 碘代三甲硅烷 作用下， 以 四氯化碳 为溶剂， 反应 2.0h， 以65%的产率得到DL-烯丙基甘氨酸甲酯
  参考文献：
  名称：

  由烯丙基硅烷和缩水甘油基阳离子等价物合成γ，δ-不饱和α-氨基酸

  摘要：

  描述了由不同的烯丙基硅烷和缩水甘油基阳离子当量6和7的偶联合成一系列的γ，δ-不饱和的N-保护的α-氨基酸甲基酯。BF 3 ·OEt 2诱导与甲氧基甘氨酸衍生物6的反应。在氯甘氨酸衍生物7的情况下，将SnCl 4用作路易斯酸。反应是完全区域选择性的，但显示出低的立体选择性。在两种情况下描述了反应产物向未保护的α-氨基酸的转化。

  DOI：

  10.1016/s0040-4020(01)89098-0
• 作为产物：
  描述：

  2-叔丁氧基羰基氨基-4-戊烯酸 在 2,6-二甲基吡啶 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 1.25h， 生成 Methyl 2-<(allyloxycarbonyl)amino>-2-methoxyacetate
  参考文献：
  名称：

  Syntheses and reactions of silyl carbamates. 1. Chemoselective transformation of amino protecting groups via tert-butyldimethylsilyl carbamates

  摘要：

  DOI：

  10.1021/jo00290a015

文献信息

• Synthesis and in vitro enzyme activity of an oxa analogue of azi-DAP
  作者：Russell J. Cox、Jeremy Durston、David I. Roper

  DOI：10.1039/b201727j

  日期：2002.4.9

  The synthesis of a novel epoxide inhibitor 6 of meso-DAP epimerase was achieved. A new and convenient assay for meso-DAP epimerase was devised which is a considerable improvement on previously reported assay methods. This assay was used to determine the inhibitory properties of 6. The epoxide 6 shows limited competitive inhibition vs. meso-DAP epimerase, but clear time dependent inhibition indicative of the expected covalent attachment at the active site. Epoxide 6, although an effective inhibitor of meso-DAP epimerase, was unstable at pH 7.3 in aqueous buffer, being hydrolysed to the corresponding diol.

  成功合成了新型环氧化物抑制剂6，用于消旋二氨基庚二酸表异构酶。设计了一种新的便捷消旋二氨基庚二酸表异构酶检测方法，相较于先前报道的检测方法有显著改进。该检测方法被用于确定抑制剂6的抑制特性。环氧化物6对消旋二氨基庚二酸表异构酶显示出有限的竞争性抑制，但存在明显的随时间递增的抑制作用，表明预期活性部位发生了共价结合。环氧化物6虽然是消旋二氨基庚二酸表异构酶的有效抑制剂，但在pH 7.3的水性缓冲液中不稳定，会水解生成对应的二醇。
• Characterization of Cyclic <i>N</i> ‐Acyliminium Ions by Infrared Ion Spectroscopy
  作者：Jona Merx、Kas J. Houthuijs、Hidde Elferink、Eva Witlox、Jasmin Mecinović、Jos Oomens、Jonathan Martens、Thomas J. Boltje、Floris P. J. T. Rutjes

  DOI：10.1002/chem.202104078

  日期：2022.2.16

  N-Acyliminium ions (NAIs) are highly reactive intermediates that are important for the construction of CC-bonds adjacent to nitrogen atoms. These species have been characterized for the first time in the gas phase by collision induced dissociation tandem mass spectrometry followed by infrared ion spectroscopy (IRIS), which has led to new structural information that can be invoked to explain the diastereoselectivity

  N-酰基胺离子 (NAI) 是高反应性中间体，对于构建与氮原子相邻的 CC 键非常重要。首次通过碰撞诱导解离串联质谱法和红外离子光谱法 (IRIS) 在气相中对这些物质进行了表征，从而获得了新的结​​构信息，可用于解释涉及这些阳离子中间体的反应的非对映选择性。
• Tertiary-butyldimethylsilyl carbamate derivative and process for
  申请人：Suntory Limited

  公开号：US04837349A1

  公开（公告）日：1989-06-06

  A t-butyldimethylsilyl carbamate derivative and a process for producing the same are disclosed. Tertiary-butyldimethylsilyl carbamate derivatives having the following general formula (1) are intermediates for the production of a variety of carbamate esters that can be extensively used as drugs acting on the central nervous system or circulatory organs, as agrichemicals (e.g. insecticides and herbicides), or as antimicrobial agents; a process capable of economical and efficient production of such intermediates is also disclosed: ##STR1## where R.sup.1 is an alkyl group having 1-3 carbon atoms or a hydrogen atom; R.sup.2 is ##STR2## (where R.sup.3 is a hydrogen atom, an alkyl, alkenyl or aralkyl group having 1-10 carbon atoms, each of which groups may be substituted by a hydroxyl group, a t-butyldimethylsilyloxy group, a methylthio group, a lower alkoxycarbonyl group, a lower alkoxy group, an indolyl group or an imidazolyl group; R.sup.4 is a lower alkoxycarbonyl group, an N-alkylamido group having 2-6 carbon atoms, an O-tetrahydropyranylthr eonine methyl ester amido residue, an O-t-butyldimethylsilylthreonine methyl ester amido residue, a threonine methyl ester amido residue or --(CH.sub.2).sub.n --COOR.sup.5 (where n is an integer of 1-3 and R.sup.5 is a lower alkyl group), provided that R.sup.3 combines with R.sup.4 to form a cyclopentyl group, a cyclohexyl group, a tetrahydrofuranyl group or a dioxanyl group, these rings being optionally substituted by a lower alkyl group, a lower alkenyl group, a lower alkoxycarbonyl group or a lower alkoxycarbonylmethyl group); and R.sup.1 and R.sup.2, when taken together, form a 4- or 5-membered carbon ring, which may be substituted by a lower alkoxycarbonyl group or a t-butyldimethylsilyloxycarbonyl group.

  本发明公开了一种t-叔丁基二甲基硅烷基氨基甲酸酯衍生物及其制备方法。具有以下通用式（1）的三叔丁基二甲基硅烷基氨基甲酸酯衍生物是制备多种可广泛用作中枢神经系统或循环器官药物、农药（例如杀虫剂和除草剂）或抗微生物剂的氨甲酯的中间体；本发明还公开了一种能够经济高效地生产这种中间体的方法： 其中，R1是具有1-3个碳原子的烷基或氢原子；R2是##STR2##（其中R3是氢原子、具有1-10个碳原子的烷基、烯基或芳基烷基，这些基团中的每一个都可以被羟基、t-叔丁基二甲基硅氧基、甲硫基、低级烷氧羰基基团、低级烷氧基、吲哚基或咪唑基取代；R4是低级烷氧羰基基团、具有2-6个碳原子的N-烷基酰胺基团、O-四氢吡喃基缩酰亮氨酸甲酯酰基、O-t-叔丁基二甲基硅基缩酰亮氨酸甲酯酰基、亮氨酸甲酯酰基或--（CH2）n--COOR5（其中n是1-3的整数，R5是低级烷基基团），前提是R3与R4结合形成环戊基、环己基、四氢呋喃基或二氧杂环己基，这些环可选地被低级烷基、低级烯基、低级烷氧羰基基团或低级烷氧羰基甲基基团取代；当R1和R2一起取时，形成一个4-或5-成员碳环，该环可以被低级烷氧羰基基团或t-叔丁基二甲基硅氧羰基基团取代。
• Tertiary-butyldimethylsilyl carbamate derivative and process for producing the same
  申请人：SUNTORY LIMITED

  公开号：EP0217243A2

  公开（公告）日：1987-04-08

  At-butyldimethylsilyl carbamate derivative and a process for producing the same are disclosed. Tertiarybutyl- dimethylsilyl carbamate derivatives having the following general formula (1) are intermediates for the production of a variety of carbamate esters that can be extensively used as drugs acting on the central nervous system or circulatory organs, as agrichemicals (e.g. insecticides and herbicides), or as antimicrobial agents; a process capable of economical and efficient production of such intermediates is also disclosed: where R1 is an alkyl group having 1 - 3 carbon atoms or a hydrogen atom; R2 is (where R3 is a hydrogen atom, an alkyl, alkenyl or aralkyl group having 1 - 10 carbon atoms, each of which groups may be substituted by a hydroxyl group, a t-butyldimethylsilyloxy group, a methylthio group, a lower alkoxycarbonyl group, a lower alkoxy group, an indolyl group or an imidazolyl group; R4 is a lower alkoxycarbonyl group, an N-alkylamido group having 2 - 6 carbon atoms, an O-tetrahydropyranylthreonine methyl ester amido residue, an O-t-butyldimethyl- silylthreonine methyl ester amido residue, a threonine methyl ester amido residue or -(CH2)n-COOR5 (where n is an integer of 1 - 3 and R5 is a lower alkyl group), provided that R3 combines with R4 to form a cyclopentyl group, a cyclohexyl group, a tetrahydrofuranyl group or a dioxanyl group, these rings being optionally substituted by a lower alkyl group, a lower alkenyl group, a lower alkoxycarbonyl group or a lower alkoxycarbonylmethyl group); and R' and R2, when taken together, form a 4- or 5-membered carbon ring, which may be substituted by a lower alkoxycarbonyl group or a t-butyldimethylsilyloxycarbonyl group.

  本发明公开了叔丁基二甲基硅基氨基甲酸酯衍生物及其生产工艺。具有以下通式(1)的叔丁基二甲基硅基氨基甲酸酯衍生物是生产各种氨基甲酸酯的中间体，这些氨基甲酸酯可广泛用作作用于中枢神经系统或循环器官的药物、农用化学品（如杀虫剂和除草剂）或抗菌剂；还公开了一种能够经济、高效地生产这种中间体的工艺： 其中 R1 是具有 1 - 3 个碳原子的烷基或氢原子；R2 是 (其中 R3 是氢原子、具有 1-10 个碳原子的烷基、烯基或芳基，每个基团可被羟基、叔丁基二甲基硅氧基、甲硫基、低级烷氧基羰基、低级烷氧基、吲哚基或咪唑基取代；R4 是低级烷氧基羰基、具有 2-6 个碳原子的 N-烷基氨基、O-四氢吡喃苏氨酸甲酯氨基残基、O-叔丁基二甲基硅基苏氨酸甲酯氨基残基、苏氨酸甲酯氨基残基或-(CH2)n-COOR5（其中 n 为 1-3 的整数，R5 为低级烷基）、条件是 R3 与 R4 结合形成环戊基、环己基、四氢呋喃基或二噁烷基，这些环可选择被低级烷基、低级烯基、低级烷氧羰基或低级烷氧羰基甲基取代）；R'和 R2 合在一起形成一个 4 或 5 元碳环，可被一个低级烷氧羰基或一个 t-丁基二甲基硅氧基羰基取代。
• Palladium-Catalyzed Transprotection of Allyloxycarbonyl-Protected Amines: Efficient One-Pot Formation of Amides and Dipeptides
  作者：Eric C. Roos、Pablo Bernabe、Henk Hiemstra、W. Nico Speckamp、Bernard Kaptein、Wilhelmus H. J. Boesten

  DOI：10.1021/jo00111a035

  日期：1995.3

  The synthetic utility of the N-(allyloxycarbonyl) (Alloc) substituent in alpha-amino acid derivatives is substantially extended beyond its well-known function as an amine protecting group. When the palladium-catalyzed deprotection is carried out by using tributyltin hydride as nucleophile (the Guibe method) in the presence of an active acylating agent a new acyl group is introduced on nitrogen. Successful acylating agents include carboxylic acid anhydrides, acid chlorides, and activated esters. A useful example of this methodology is the removal of the Alloc group in the presence of tert-butyl dicarbonate, which in essence amounts to a ''transprotection'' to a Boc-protected alpha-amino acid derivative. More importantly, the use of activated N-protected alpha-amino ester derivatives (e.g., pentafluorophenyl esters) leads to dipeptides. This new method for peptide coupling proceeds very fast under mild conditions, in good to excellent yields, and without noticeable racemization.