ethyl 2-azido-2-methyl-3-oxo-3-phenylpropanoate | 235096-50-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2-azido-2-methyl-3-oxo-3-phenylpropanoate
• CAS: 235096-50-1
• 化学式: C₁₂H₁₃N₃O₃
• 分子量: 247.254
• InChiKey: ZFFVIKVNAYTXTA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  57.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 2-azido-2-methyl-3-oxo-3-phenylpropanoate 在 iron(II) bromide 、 N-((2Z,4E)-4-(mesitylimino)pent-2-en-2-yl)-2,4,6-trimethylaniline 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以26%的产率得到ethyl 2-benzamidoacrylate
  参考文献：
  名称：

  铁催化的叔α-叠氮基酮的酰基迁移：酰胺和异喹诺酮类化合物的合成方法。

  摘要：

  本文报道，在较高的温度下，通过在DMF中用FeBr 2处理，可以将叔α-叠氮基苯基酮转化为酰胺。该反应通过从α-碳到氮原子的1，2-苯甲酰基迁移而伴随着氮分子的排出而进行。该方案适用于合成N-（环戊-1-烯-1-基）苯甲酰胺，N-（环己-1-烯-1-基）苯甲酰胺和N-苯甲酰基-α-甲基烯胺。异喹诺酮类的简便治疗方法。

  DOI：

  10.1021/acs.orglett.8b00409
• 作为产物：
  描述：

  2-甲基-3-氧代-3-苯基丙酸乙酯 在 N-溴代丁二酰亚胺(NBS) 、 sodium azide 、 magnesium(II) perchlorate 作用下， 以 二甲基亚砜 、 乙腈 为溶剂， 反应 6.0h， 生成 ethyl 2-azido-2-methyl-3-oxo-3-phenylpropanoate
  参考文献：
  名称：

  铁催化的叔α-叠氮基酮的酰基迁移：酰胺和异喹诺酮类化合物的合成方法。

  摘要：

  本文报道，在较高的温度下，通过在DMF中用FeBr 2处理，可以将叔α-叠氮基苯基酮转化为酰胺。该反应通过从α-碳到氮原子的1，2-苯甲酰基迁移而伴随着氮分子的排出而进行。该方案适用于合成N-（环戊-1-烯-1-基）苯甲酰胺，N-（环己-1-烯-1-基）苯甲酰胺和N-苯甲酰基-α-甲基烯胺。异喹诺酮类的简便治疗方法。

  DOI：

  10.1021/acs.orglett.8b00409

文献信息

• Stereoselectivity in reactions of amino acids catalyzed by pyridoxal derivatives carrying rigidly-Attached chirally-Mounted basic groups—transamination, racemization, decarboxylation, retro-Aldol reaction, and aldol condensation
  作者：Lei Liu、Mary Rozenman、Ronald Breslow

  DOI：10.1016/s0968-0896(02)00334-6

  日期：2002.12

  groups of pyridoxal, and also two examples of rigidly held chirally mounted basic groups. They were able to selectively catalyze decarboxylation, aldol reaction, and retro-aldol reaction of amino acids rather than transamination, and with stereoselectivity. In the aldol reaction of glycine with acetaldehyde to synthesize threonine and allo-threonine, one of the catalysts reversed its stereoselectivity

  四氢喹啉环用于安装吡ido醛的关键官能团，以及两个刚性固定的手性安装的碱性基团的例子。他们能够选择性催化氨基酸的脱羧，醛醇反应和逆醛醇反应，而不是氨基转移，并且具有立体选择性。在甘氨酸与乙醛的醛醇缩醛反应中合成苏氨酸和异苏氨酸，当碱性基团被质子化时，其中一种催化剂逆转了其立体选择性。观察到的立体选择性均与预测一致。
• Addition/Cycloaddition of Acetylenedicarboxylates to Open-Chain or Cyclic Amino Carbonyl Compounds
  作者：Giacomo Guerrini、Fabio Ponticelli

  DOI：10.1002/ejoc.201000371

  日期：——

  Some new, interesting, and unknown heterocyclic rings and open-chain molecules have been obtained with ease and under mild conditions by reaction of a wide range of amino carbonyl compounds with acetylenic esters. The reactivity is highly dependent on the substituents and their positions in the starting material, which can be either cyclic (pyrazolones) or open-chain compounds.

  一些新的、有趣的和未知的杂环和开链分子已经通过广泛的氨基羰基化合物与炔酸酯的反应在温和的条件下轻松获得。反应性高度依赖于取代基及其在原料中的位置，原料可以是环状（吡唑啉酮）或开链化合物。
• Reactions of Benzocyclic β-Keto Esters with Sulfonyl Azides. 2.¹ Further Insight into the Influence of Azide Structure and Solvent on the Reaction Course
  作者：Luisa Benati、Daniele Nanni、Piero Spagnolo

  DOI：10.1021/jo9901541

  日期：1999.7.1

  The reactions of 2-ethoxycarbonyl-1-benzosuberone, with 4-methoxybenzenesulfonyl, 2,4,6-triiso-propylbenzenesulfonyl, methanesulfonyl, and trifluoromethanesulfonyl azide, in the presence of triethylamine, have been investigated in N,N-dimethylformamide, acetonitrile, or tetrahydrofuran with the intent of clarifying the influence of both the azide electrophile and solvent on the reaction course. The present findings, in addition to those previously obtained with tosyl and 4-nitrobenzenesulfonyl azide, indicate that both the electronic features of the sulfonyl azide and the solvent polarity greatly affect the possible occurrence of azidation and/or Favorskii-type ring contraction at the expense of deacylating diazo transfer. Azidation is promoted by the less electrophilic azides, while it is virtually avoided by the more electrophilic ones. Ring contraction occurs to a limited extent with the less electrophilic azides, but it becomes the main process with those more electrophilic. Moreover, azidation is virtually unaffected by the solvent polarity, while ring contraction can markedly be enhanced by a highly polar solvent. Firm evidence has additionally been obtained that, in contrast to a previous claim, trifluoromethanesulfonyl azide can normally perform diazotization of acyclic beta-keto esters in preference to azidation.
• Unified Strategy for Iodine(III)-Mediated Halogenation and Azidation of 1,3-Dicarbonyl Compounds
  作者：Marc J. Galligan、Ramulu Akula、Hasim Ibrahim

  DOI：10.1021/ol403504z

  日期：2014.1.17

  A mild and rapid (diacetoxyiodo)benzene-mediated formal electrophilic alpha-azidation of 1,3-dicarbonyl compounds using commercially available Bu4NN3 as the azide source is reported. The reaction conditions employed are based on optimization studies conducted on the analogous halogenations with Et4NX (X = Cl, Br, 1).
• Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. A Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion
  作者：Luisa Benati、Daniele Nanni、Corrado Sangiorgi、Piero Spagnolo

  DOI：10.1021/jo990837g

  日期：1999.10.1

  A variety of acyclic and carbocyclic alpha-azido-beta-keto esters have been readily prepared from the parent dicarbonyl compounds, and their radical chain reactions with tributyltin hydride have been investigated. These reactions normally result in efficient production of alkoxycarbonyl-substituted amides and lactams and thence provide a new, useful method for regiospecific nitrogen insertion of keto ester compounds. The likely mechanism entails initial addition of tributylstannyl radical to the azido moiety to give a stannylaminyl radical, which readily undergoes intramolecular three-membered cyclization onto the ketone group to form an alkoxyl radical. The alkoxyl radical then undergoes regiospecific beta-scissian to form a stable ring-opened radical that is eventually reduced by tributyltin hydride to propagate the chain. With certain substrates, concomitant deazidation occurs to an important extent. This process, which is unusually observed in radical reactions of alkyl azides, is ascribed to addition of the stannyl radical to the terminal azido nitrogen; subsequent fragmentation of the ensuing 1,3-triazenyl adduct gives stannyl azide and a deazidated alkyl radical, resonance-stabilized by the adjacent carbonyl groups. The radical reactions of 2-azido-2-(ethoxy-carbonyl)-1-tetralone with allyltributylstannane and allyltriphenylstannane have also been investigated with the (missed) aim to achieve nitrogen insertion and concomitant allylation.