methyl 6-{[(benzyloxy)carbonyl]amino}-2-diazohexanoate | 82830-85-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 6-{[(benzyloxy)carbonyl]amino}-2-diazohexanoate
• 英文别名: methyl (2Z)-2-diazo-6-(phenylmethoxycarbonylamino)hexanoate
• CAS: 82830-85-1
• 化学式: C₁₅H₁₉N₃O₄
• 分子量: 305.334
• InChiKey: FNSCXDFRZVKLKW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  22
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  66.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 6-{[(benzyloxy)carbonyl]amino}-2-diazohexanoate 在 三丁基膦 作用下， 以 异丙醇 为溶剂， 反应 2.5h， 生成 methyl (E)-2-hydrazono-6-benzyloxycarbonylaminohexanoate
  参考文献：
  名称：

  A novel method for the synthesis of 3,4-disubstitutedpyrrole-2,5-dicarboxylates from hydrazones derived from α-diazo esters

  摘要：

  Hydrazones obtained from alpha-diazo esters were converted to pyrroles when heated with thionyl chloride in alcohol. Among hydrazones, those substituted with a benzene ring on the beta-carbon to the ester are likely to give pyrroles in good yields. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.03.037
• 作为产物：
  描述：

  N-苄氧羰基--6-氨基己酸 在 硫酸 作用下， 生成 methyl 6-{[(benzyloxy)carbonyl]amino}-2-diazohexanoate
  参考文献：
  名称：

  Asymmetric catalysis of intramolecular N–H insertion reactions of α-diazocarbonyls

  摘要：

  Intramolecular N-H insertion reactions of alpha-diazocarbonyl substrates are catalysed by rhodium(II) carboxylates with catalyst-dependent competition with C-H insertion and beta-elimination; asymmetric N-H insertion leading to a pipecolic acid derivative with ee up to 45% is achieved using chiral catalysts.

  DOI：

  10.1039/cc9960001465

文献信息

• PREPARATION OF DIAZO AND DIAZONIUM COMPOUNDS
  申请人：Raines Ronald Thaddeus

  公开号：US20100125132A1

  公开（公告）日：2010-05-20

  A method for making diazo-compounds, diazonium salts thereof and other protected forms of these compounds. Diaz-compounds are prepared by reaction of a tertiary phosphine reagent carrying a reactive carbonyl group with an azide. The reaction can also generate an acyl triazene which can be converted thermally or by addition of base to form the diazo-compound or the acyl triazene can be isolated. The method is particularly useful for conversion of azides carrying one or more electron withdrawing groups to diazo-compounds. The method can be carried out in aqueous medium under mild conditions and is particularly useful for conversion of azido sugars to diazo-compound and diazonium salts thereof under physiological conditions. Tertiary phosphine reagents, particularly those that are water-soluble, and precursors for preparation of the reagents are provided.

  一种制备重氮化合物、其重氮盐和这些化合物的其他保护形式的方法。通过将携带反应性羰基基团的三级膦试剂与偶氮化物反应来制备重氮化合物。该反应还可以生成酰基三氮烯，可以通过热转化或加入碱来形成重氮化合物，或者可以分离出酰基三氮烯。该方法特别适用于将携带一个或多个电子吸引基团的偶氮化物转化为重氮化合物。该方法可以在温和条件下在水性介质中进行，并且特别适用于在生理条件下将偶氮糖转化为重氮化合物和其重氮盐。提供了三级膦试剂，特别是那些水溶性的试剂，以及用于制备这些试剂的前体。
• Novel approach to arylhydrazones, the precursor for Fischer indole synthesis, via diazo esters derived from α-amino acid esters
  作者：Eiko Yasui、Masao Wada、Norio Takamura

  DOI：10.1016/j.tetlet.2005.11.126

  日期：2006.1

  A novel method for synthesizing arylhydrazones, the precursor for Fischer indole synthesis, using aryllithium reagents and α-diazo esters that are easily obtained from α-amino acid esters, is described.

  描述了一种新颖的方法，该方法使用芳基锂试剂和容易从α-氨基酸酯获得的α-重氮酯来合成费歇尔吲哚合成的前体芳基hydr。
• New Entry for Synthesis of N-Acylhydrazones, Pyridazinones, and 1,3,4-Oxadiazin-6-ones from .ALPHA.-Amino Acid Esters
  作者：Eiko Yasui、Masao Wada、Norio Takamura

  DOI：10.1248/cpb.55.1652

  日期：——

  Versatile electrophiles N-acylhydrazones are synthesized via diazotization, reduction, and acylation of α-amino acid esters. Reduction of diazo esters with L-selectride® or tributylphosphine affords the corresponding hydrazones in good yields. Both reducing agents give anti-hydrazones as the major product although the reactivity of each reductant is slightly different. The resulting hydrazones are acylated to give N-acylhydrazones, which are subjected to further reactions to give 1,3,4-oxadiazin-6-ones that serve as useful synthetic intermediates for the Diels–Alder reaction.

  通过对 α-氨基酸酯进行重氮化、还原和酰化，可合成多功能亲电体 N-酰肼。用 L-selectride® 或三丁基膦还原重氮酯，可以得到相应的肼，而且收率很高。尽管每种还原剂的反应性略有不同，但两种还原剂都会产生主要产物反肼。生成的肼经酰化后可得到 N-酰肼，再经进一步反应可得到 1,3,4-恶二嗪-6-酮，它们是 Diels-Alder 反应的有用合成中间体。
• Novel method for synthesis of aryl hydrazones from α-diazo esters: scope and limitations of nucleophiles
  作者：Eiko Yasui、Masao Wada、Norio Takamura

  DOI：10.1016/j.tet.2008.11.028

  日期：2009.1

  Aryl hydrazones, the precursor of Fischer indole synthesis, were easily obtained by nucleophilic addition of aryllithium reagents to diazo esters. The aryl hydrazones were converted into indoles in good yields by heating with thionyl chloride in alcohol. Grignard reagent was also a good nucleophile, whereas organozinc reagent did not react with diazo esters. Aryllithium reagents were prepared by reacting

  通过芳基锂试剂向重氮酯的亲核加成，很容易获得费歇尔吲哚合成的前体芳基hydr。通过与亚硫酰氯在醇中加热，将芳基酮以良好的产率转化为吲哚。格氏试剂也是良好的亲核试剂，而有机锌试剂则不会与重氮酯反应。芳基锂试剂是通过使在2-，3-，4-或多位具有各种取代基的芳基溴化物与n- BuLi反应制得的。将衍生自溴吡啶的亲核试剂加到重氮酯中也得到。
• Preparation of diazo and diazonium compounds
  申请人：Wisconsin Alumni Research Foundation

  公开号：US08350014B2

  公开（公告）日：2013-01-08

  A method for making diazo-compounds, diazonium salts thereof and other protected forms of these compounds. Diaz-compounds are prepared by reaction of a tertiary phosphine reagent carrying a reactive carbonyl group with an azide. The reaction can also generate an acyl triazene which can be converted thermally or by addition of base to form the diazo-compound or the acyl triazene can be isolated. The method is particularly useful for conversion of azides carrying one or more electron withdrawing groups to diazo-compounds. The method can be carried out in aqueous medium under mild conditions and is particularly useful for conversion of azido sugars to diazo-compound and diazonium salts thereof under physiological conditions. Tertiary phosphine reagents, particularly those that are water-soluble, and precursors for preparation of the reagents are provided.

  一种制备重氮化合物、重氮盐及这些化合物的其他保护形式的方法。通过将带有反应性羰基基团的三级膦试剂与叠氮化合物反应制备重氮化合物。该反应也可以生成酰基三氮烯，可通过热转化或加入碱来形成重氮化合物，或可将酰基三氮烯分离。该方法特别适用于将带有一个或多个电子吸引基团的叠氮化合物转化为重氮化合物。该方法可在温和条件下在水介质中进行，并且特别适用于在生理条件下将叠氮糖转化为重氮化合物和重氮盐。提供了三级膦试剂，特别是水溶性的试剂及其制备前体。