benzyl 3-bromopropiolate | 87598-76-3

• 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: benzyl 3-bromopropiolate
• 英文别名: Benzyl 3-bromoprop-2-ynoate；benzyl 3-bromoprop-2-ynoate
• CAS: 87598-76-3
• 化学式: C₁₀H₇BrO₂
• 分子量: 239.068
• InChiKey: JHYNODHGRZPXDQ-UHFFFAOYSA-N

物化性质

• 沸点：
  302.7±35.0 °C(Predicted)
• 密度：
  1.540±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  benzyl 3-bromopropiolate 在 sodium periodate 、 copper diacetate 、 邻苯三酚 作用下， 以 甲醇 、 乙醚 、 水 为溶剂， 反应 25.5h， 生成 6-{(3S,4S,5S,7S)-7-[(2R,3R,5R)-5-Ethyl-5-((2S,5S,6R)-5-ethyl-5-hydroxy-6-methyl-tetrahydro-pyran-2-yl)-3-methyl-tetrahydro-furan-2-yl]-4-hydroxy-3,5-dimethyl-6-oxo-nonyl}-2-hydroxy-3-methyl-benzoic acid benzyl ester
  参考文献：
  名称：

  Total synthesis of polyether antibiotics. Synthesis of the enantiomer of lasalocid A (X-537A)

  摘要：

  DOI：

  10.1021/jo00174a008
• 作为产物：
  描述：

  丙炔酸苄酯 在 N-溴代丁二酰亚胺(NBS) 、 silver nitrate 作用下， 以 丙酮 为溶剂， 反应 2.0h， 以83%的产率得到benzyl 3-bromopropiolate
  参考文献：
  名称：

  Direct Spirocyclization from Keto-sulfonamides: An Approach to Azaspiro Compounds

  摘要：

  Spontaneous spirocyclization of keto-sulfonamides via ynamides through a one-pot process is presented. Push pull ynamides were obtained through Michael addition/elimination without Cu. The obtained azaspiro compounds are building blocks for indole alkaloids. Theoretical studies provide insights into the mechanism of the formal Conia-ene reaction.

  DOI：

  10.1021/acs.orglett.7b02216

文献信息

• Access to Cyclobutene-Fused Azepines through Au-Catalyzed Cycloisomerization of Stable Alkyne Tethered Ketene <i>N,N</i>-Acetals
  作者：Sanatan Nayak、Nayan Ghosh、Akhila K. Sahoo

  DOI：10.1021/ol501125r

  日期：2014.6.6

  base promoted reaction between N-protected propargyl amines and 3-bromopropiolate readily provides an array of novel stable alkyne-tethered ketene N,N-acetals in good yields. A wide range of structurally complex cyclobutene-fused azepine heterocycles are synthesized through the gold-catalyzed intramolecular cycloisomerization of ketene N,N-acetals for the first time. A plausible reaction pathway is deduced

  N-保护的炔丙基胺和3-溴丙酸酯之间的碱促进的反应容易以良好的产率提供了一系列新型的稳定的炔烃系链烯酮N，N-乙缩醛。首次通过金催化乙烯酮N，N-乙缩醛的分子内环异构化反应，合成了多种结构复杂的环丁烯稠合的ze庚因杂环。根据1 H NMR研究推论出可能的反应途径。
• A Novel Fragmentation of 7-Azabicyclo[2.2.1]hepta-2,5-dienes: Synthesis of<i>cis</i>-5-Amidino-pyrrolidine-2-acetic Acid Derivatives
  作者：Volkhard Austel、Dirk Weber、Eberhard Heller、Christoph Hoenke、Stefan Hörer、Peter Bäuerle

  DOI：10.1055/s-2005-870011

  日期：——

  A new fragmentation reaction of 3-bromo-7-azabicy­clo[2.2.1]hepta-2,5-diene carboxylic esters with 2-amino or 2-aminomethyl anilines is described. It leads to cis-5-(benzimidazol-2-yl)- or cis-5-(3,4-dihydroquinazolin-2-yl)-pyrroline-2-acetic acid esters. Substituents on the nitrogen atoms or in the aromatic ring are tolerated as long as they do not strongly reduce the nucleophilicity of the nitrogen atoms. The primary reaction products are not very stable but hydrogenation of the pyrroline and/or cleavage of the ester give products that are suitable for subsequent structural modifications, particularly ones that are interesting for combinatorial syntheses.

  描述了一种新型的3-溴-7-氮杂环庚-2,5-二烯羧酸酯与2-氨基或2-氨基甲基苯胺的裂解反应。该反应生成的产物为顺式-5-(苯并咪唑-2-基)或顺式-5-(3,4-二氢喹唑啉-2-基)-吡咯啉-2-乙酸酯。只要不显著降低氮原子的亲核性，氮原子上的取代基或芳香环中的取代基均可耐受。初级反应产物相对不稳定，但对吡咯啉进行氢化和/或对酯的裂解则可以得到适合后续结构修饰的产物，特别是对组合合成有趣的产物。
• A convenient route to alkyl, alkynyl and aryl substituted 7-azabicyclo[2.2.1]heptadienes
  作者：Chunming Zhang、Mark L Trudell

  DOI：10.1016/s0040-4020(98)00466-9

  日期：1998.7

  3-Bromopropiolates underwent a smooth [4+2] cycloaddition reaction with N-acylpyrroles to afford N-acyl-2-alkoxycarbonyl-3-bromo-7-azabicyclo[2.2.1]heptadienes in good yields. The 3-bromo-2,7-dimethoxycarbonyl-7-azabicyclo[2.2.1]heptadiene was further transformed to 3-alkyl-, 3-alkynyl- and 3-aryl-2,7-dimethoxycarbonyl-7-azabicyclo[2.2.1]heptadiene derivatives via palladium catalyzed and organocopper

  3-Bromopropiolates接受具有光滑[4 + 2]环加成反应Ñ -acylpyrroles得到Ñ酰基-2-烷氧羰基-3-溴-7-氮杂双环[2.2.1]以良好的收率heptadienes。将3-溴-2,7-二甲氧基羰基-7-氮杂双环[2.2.1]庚二烯进一步转化为3-烷基-，3-炔基-和3-芳基-2,7-二甲氧基羰基-7-氮杂双环[2.2。 1]庚二烯衍生物通过钯催化和有机铜偶联反应。
• Direct synthesis of butadiynyl-substituted pyrroles under solvent- and transition metal-free conditions
  作者：Denis N. Tomilin、Bartłomiej Pigulski、Nurbey Gulia、Agata Arendt、Lyubov N. Sobenina、Al'bina I. Mikhaleva、Sławomir Szafert、Boris A. Trofimov

  DOI：10.1039/c5ra08820h

  日期：——

  mechanochemical approach covers 4,5,6,7-tetrahydro-1H-indole, its N-substituted derivatives and 2-phenylpyrrole and on the other hand ester and phenyl end-capped 1-halobutadiynes including chlorides, bromides and iodides. Interestingly, the method has proven effective also for weak electron withdrawing aryl substituted 1-halobutadiynes what has not been yet achieved for 1-haloacetylenes. Such reactivity

  这项工作描述了使用1-卤代丁二炔方便，高效地进行取代吡咯的CH丁二酰化反应。该方法仅需在研钵中在温和，无溶剂和无过渡金属的条件下简单研磨基质，即可构成使用1-卤代丁二炔通过交叉偶联反应进行吡咯丁二酰化的第一个实例。这种机械化学方法的范围包括4,5,6,7-四氢-1 H-吲哚，其N-取代的衍生物和2-苯基吡咯，以及另一方面为酯和苯基封端的1-卤代丁二炔，包括氯化物，溴化物和碘化物。有趣的是，该方法已证明对于弱电子吸取芳基取代的1-卤代丁二炔也有效，而1-卤代乙炔尚未实现。从文献数据的角度来看，这种反应性是出乎意料的，并为有机合成包括药物合成的众多底物打开了大门。还介绍了两个耦合产品的X射线分析。
• Trapping of <i>N</i>-Acyliminium Ions with Enamides: An Approach to Medium-Sized Diaza-Heterocycles
  作者：Lucile Andna、Laurence Miesch

  DOI：10.1021/acs.orglett.8b01407

  日期：2018.6.1

  Enamides equipped with N-acyliminium ion precursors were obtained through reduction of ynamides tethered to N-imides. Intramolecular TMSOTf-mediated trapping of N-acyliminium ions provided a variety of polyfunctionalized medium-sized diaza-heterocycles of putative pharmacological interest.