ethyl 2-diazo-6-hydroxy-3-oxohexanoate | 122060-92-8

• 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: ethyl 2-diazo-6-hydroxy-3-oxohexanoate
• 英文别名: ethyl (2Z)-2-diazo-6-hydroxy-3-oxohexanoate
• CAS: 122060-92-8
• 化学式: C₈H₁₂N₂O₄
• 分子量: 200.194
• InChiKey: HJOBQHZFGLOOLB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  65.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 2-diazo-6-hydroxy-3-oxohexanoate 在 rhodium(II) acetate dimer sodium acetate 、 magnesium sulfate 、 potassium carbonate 、 丁炔二酸二甲酯 、 pyridinium chlorochromate 作用下， 以 乙醚 、 二氯甲烷 、 苯 为溶剂， 反应 31.0h， 生成 3-羟基吡啶甲酸乙酯
  参考文献：
  名称：

  Synthesis of Functionalized Azomethine Ylides via the Rh(II)-Catalyzed Cyclization of .alpha.-Diazo Carbonyls onto Imino .pi.-Bonds

  摘要：

  alpha-Diazo carbonyl compounds containing an imino group in the gamma-position have been found to undergo a rhodium(II) acetate induced cyclization reaction to generate cyclic azomethine ylides. The reactive dipole undergoes a subsequent 1,3-dipolar cycloaddition with added dipolarophiles. The imino/oxime nitrogen lone pair of electrons must be properly oriented so as to interact with the rhodium carbenoid. Thus, acyclic oxime ethers which exist in the proper E-configuration readily undergo the tandem cyclization-cycloaddition reaction. In sharp contrast, the isomeric Z-oximino diazo carbonyl system does not cyclize to an azomethine ylide but rather intramolecularly inserts into the oximino C-H bond. Addition of a catalytic amount of rhodium(II) acetate to (E)-2-(diazoacetyl)benzaldehyde O-methyloxime in the presence of DMAD or N-phenylmaleimide affords a dipolar cycloadduct in high yield. When p-quinone was used as the dipolarophile, the initially formed cycloadduct was treated with acetic anhydride to give a compound containing the basic core dibenzo[a,d]cyclohepten-5,10-imine skeleton found in MK-801. Cyclic imines such as isoxazolines were particularly effective substrates for azomethine ylide formation. The rhodium(II) catalyzed reaction of 3-(4-diazo-3-oxobutyl)-5-phenyl-Delta(2)-isoxazoline with DMAD produced a 4:1 mixture of diastereomeric cycloadducts in good yield. Cyclization of the rhodium carbenoid did not occur with the aromatic isoxazole system and this is presumably due to the low basicity of the nitrogen lone pair of electrons.

  DOI：

  10.1021/jo00097a042
• 作为产物：
  描述：

  6-(tert-butyl-dimethyl-silanyloxy)-2-diazo-3-oxo-hexanoic acid ethyl ester 在 水 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 以89%的产率得到ethyl 2-diazo-6-hydroxy-3-oxohexanoate
  参考文献：
  名称：

  用于[2,3]-σ重排反应的一类新的铵盐：烯-内-螺盐。

  摘要：

  报道了烯-内-螺环，四氢吡啶衍生的铵碘的σ重排的第一个例子。因此，螺[6.7]-基团主要通过[2,3]-途径重排，而类似的[6.6]-基团通过[1,2]-和[2,3]-机理以大致相等的比例重排。该方法可快速进入一系列带有吡咯并[1,2-a]氮杂或八氢吲哚并核的生物碱的核心。

  DOI：

  10.1021/ol050691+

文献信息

• SUBSTITUTED BICYCLIC PYRAZOLE COMPOUNDS AS RORgammaT INHIBITORS AND USES THEREOF
  申请人：Merck Sharp & Dohme Corp.

  公开号：US20180305320A1

  公开（公告）日：2018-10-25

  The present invention relates to compounds according to Formula I: and pharmaceutically acceptable salts thereof. Such compounds can be used in the treatment of RORgammaT-mediated diseases or conditions.

  本发明涉及式I化合物：以及药用可接受的盐。此类化合物可用于治疗RORgammaT介导的疾病或状况。
• SUBSTITUTED PYRAZOLE COMPOUNDS AS RORgammaT INHIBITORS AND USES THEREOF
  申请人：Merck Sharp & Dohme Corp.

  公开号：US20180016239A1

  公开（公告）日：2018-01-18

  The present invention relates to compounds according to Formula (I-1) and pharmaceutically acceptable salts thereof. Such compounds can be used in the treatment of RORgammaT-mediated diseases or conditions.

  本发明涉及按照式(I-1)的化合物及其药用可接受的盐。这些化合物可用于治疗RORgammaT介导的疾病或症状。
• Ethyl Lithiodiazoacetate: Extremely Unstable Intermediate Handled Efficiently in Flow
  作者：Simon T. R. Müller、Tobias Hokamp、Svenja Ehrmann、Paul Hellier、Thomas Wirth

  DOI：10.1002/chem.201602133

  日期：2016.8.16

  The generated ethyl lithiodiazoacetate is highly reactive and decomposes rapidly, even at low temperatures. Herein, we report a continuous flow protocol that overcomes the problems associated with the instantaneous decomposition of ethyl lithiodiazoacetate. The addition of ethyl lithiodiazoacetate to ketones provides direct access to tertiary diazoalcohols in good yields.

  重氮乙酸乙酯（EDA）是最著名的重氮试剂之一。它常用于金属-卡宾型反应中。但是，EDA也可以在碱催化下用作亲核试剂。尽管可以使用有机碱将EDA添加到醛中，但将EDA添加到其他羰基亲电试剂中则需要使用有机金属化合物，例如二异丙基氨基化锂（LDA）。生成的硫代重氮基乙酸乙酯具有很高的反应活性，即使在低温下也能迅速分解。在此，我们报告了一种连续流方案，该方案克服了与硫代重氮基乙酸乙酯的瞬时分解有关的问题。将硫代重氮乙酸乙酯加到酮中可直接获得叔重氮醇，收率很高。
• [EN] DIHYDROPYRANOPYRIMIDINES FOR THE TREATMENT OF VIRAL INFECTIONS<br/>[FR] DIHYDROPYRANOPYRIMIDINES POUR LE TRAITEMENT D'INFECTIONS VIRALES
  申请人：JANSSEN SCIENCES IRELAND UC

  公开号：WO2018002319A1

  公开（公告）日：2018-01-04

  This invention relates to dihydropyranopynmidine derivatives, processes for their preparation, pharmaceutical compositions, and their use in treating viral infections.

  本发明涉及二氢吡喃吡啶啉衍生物，其制备方法，药物组合物以及它们在治疗病毒感染中的应用。
• An enantioselective approach to the Securinega alkaloids: the total synthesis of (+)-norsecurinine and (+)-allonorsecurinine
  作者：Matthew R. Medeiros、John L. Wood

  DOI：10.1016/j.tet.2010.03.015

  日期：2010.6

  Total syntheses of (+)-norsecurinine and (+)-allonorsecurinine are described that utilize a rhodium carbenoid-initiated O–H insertion/Claisen rearrangement/1,2-allyl migration domino process for the stereoselective introduction of the tertiary alcohol moiety. Overall the employed strategy is flexible and will allow access to other members of the Securinega family of alkaloids.

  (+)-norsecurinine 和 (+)-allonorsecurinine 的全合成描述了利用铑卡宾启动的 O-H 插入/Claisen 重排/1,2-烯丙基迁移多米诺过程来立体选择性地引入叔醇部分。总体而言，所采用的策略是灵活的，将允许访问Securinega生物碱家族的其他成员。