2,2-dimethylpent-4-ynoyl chloride | 131752-83-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: 2,2-dimethylpent-4-ynoyl chloride
• 英文别名: 2,2-dimethyl-4-pentynoyl chloride；2,2-Dimethylpent-4-ynoyl chloride
• CAS: 131752-83-5
• 化学式: C₇H₉ClO
• mdl: MFCD25957918
• 分子量: 144.601
• InChiKey: RBNNFEXMRCJUNW-UHFFFAOYSA-N

物化性质

• 沸点：
  165.8±23.0 °C(Predicted)
• 密度：
  1.060±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.571
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2-dimethylpent-4-ynoyl chloride 在 aluminum (III) chloride 、 lithium aluminium tetrahydride 作用下， 以 二氯甲烷 为溶剂， 反应 1.67h， 生成 4,4-dimethyl-1-trimethylsilanyl-hepta-1,6-diyn-3-ol
  参考文献：
  名称：

  海洋伊豆藻类鳞翅目I，L，M，N和C的总合成

  摘要：

  对映纯三炔的模块组装与强大的铑催化的[2 + 2 + 2]炔烃环三聚反应相结合，为一组新的高效鳞翅目动物毒素打开了大门，包括首次完整合成鳞翅目细菌素L，M和C 。

  DOI：

  10.1021/ol102432q
• 作为产物：
  描述：

  2,2-二甲基戊-4-炔酸 在 草酰氯 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.25h， 生成 2,2-dimethylpent-4-ynoyl chloride
  参考文献：
  名称：

  可见光介导的酰胺基自由基的 5-exo-dig 环化

  摘要：

  报道了 5-亚甲基-吡咯烷酮的可见光介导合成。这构成了第一个报道的涉及氮中心自由基的 5-exo-dig 加氢胺化反应的例子。

  DOI：

  10.1002/ejoc.201601607

文献信息

• Novel Ag(I)-catalysis of an intramolecular 1,3-dipolar cycloaddition
  作者：Andrew S. Kende、Michel Journet

  DOI：10.1016/0040-4039(95)00470-w

  日期：1995.5

  Acetylenic α-diazoketones, bearing gem-dimethyl substituents in the α′ position, were found to undergo an intramolecular 1,3-dipolar cycloaddition reaction in the presence of silver(I) as catalyst. In that instance, bicyclic pyrazole derivatives were isolated in 47 to 55% yield, even in the conditions of the Arndt-Eistert reaction. The requirement for gem-dimethyl substitution in acyclic substrates is rationalized

  发现在银（I）作为催化剂的存在下，在α'位置带有宝石-二甲基取代基的乙炔α-二氮杂环酮发生分子内的1,3-偶极环加成反应。在这种情况下，即使在Arndt-Eistert反应条件下，也以47％至55％的收率分离出双环吡唑衍生物。根据过渡态对构象能的空间效应，合理化了无环底物中对宝石二甲基取代的要求。
• An improved synthesis of α,β-unsaturated nitrones relevant to the stephacidins and analogs thereof
  作者：Benjamin D. Hafensteiner、María Escribano、Elena Petricci、Phil S. Baran

  DOI：10.1016/j.bmcl.2009.04.045

  日期：2009.7

  A new method is reported for the synthesis of the α,β-unsaturated nitrone moiety characteristic of the stephacidin/avrainvillamide family of bioactive prenylated indole alkaloids. Application to the synthesis of stephacidin analogs and a potential biological probe are showcased.

  报道了一种合成具有生物活性异戊二烯化吲哚生物碱的 stepphacidin/avrainvillamide 家族特征的 α,β-不饱和硝酮部分的新方法。展示了在 stepphacidin 类似物合成中的应用和潜在的生物探针。
• Synthetic and Theoretical Studies on Group-Transfer Imidoylation of Organotellurium Compounds. Remarkable Reactivity of Isonitriles in Comparison with Carbon Monoxide in Radical-Mediated Reactions
  作者：Shigeru Yamago、Hiroshi Miyazoe、Ryuta Goto、Masahiro Hashidume、Takashi Sawazaki、Jun-ichi Yoshida

  DOI：10.1021/ja003879r

  日期：2001.4.1

  Imidoylation of organotellurium compounds with isonitriles has been investigated in conjunction with the radical-mediated C1 homologation reaction by using CO and isonitriles. Carbon-centered radicals generated photochemically or thermally from organotellurium compounds react with isonitriles in a group-transfer manner to give the corresponding imidoylated products. Organotellurium compounds have been found to serve as effective precursors of a wide variety of stabilized radicals, namely benzyl, alpha -alkoxy, alpha -amino, and acyl radicals, which take part in the imidoylation with high efficiency. The reactions are compatible with various functional groups, and can be carried out in various solvents including environmentally benign water. The reactivity of isonitriles has been compared with that of CO through competition experiments, and the results indicate that isonitriles are superior to CO as radical accepters in reactions with stabilized radicals. The origin of the differences has been addressed in theoretical studies with density functional theory calculations using the B3LYP hybrid functional. The calculations suggest that both carbonylation and imidoylation proceed with low activation energies, and that there an virtually no differences in the kinetic sense, instead, it indicates that thermodynamic effects, namely differences in the stability of the acyl and the imidoyl radicals, control the overall course of the reactions.
• Palladium-Catalyzed Intramolecular Selenocarbamoylation of Alkynes with Carbamoselenoates:  Formation of α-Alkylidene-β-lactam Framework
  作者：Masashi Toyofuku、Shin-ich Fujiwara、Tsutomu Shin-ike、Hitoshi Kuniyasu、Nobuaki Kambe

  DOI：10.1021/ja052175k

  日期：2005.7.13

  Pd-catalyzed intramolecular selenocarbamoylation of alkynes leading to alpha-alkylidene-beta-lactams was developed. This reaction can be applied to thiocarbamoylation and to the synthesis of delta- and epsilon-lactams and a cyclobutanone.
• Total Syntheses of the Marine Illudalanes Alcyopterosin I, L, M, N, and C
  作者：Tania Welsch、Huu-Anh Tran、Bernhard Witulski

  DOI：10.1021/ol102432q

  日期：2010.12.17

  The combination of a modular assembly of enantiopure triynes and a powerful rhodium-catalyzed [2 + 2 + 2] alkyne cyclotrimerization reaction opens new and efficient entries to a set of alcyopterosins, including the first total synthesis of the alcyopterosins L, M, and C.

  对映纯三炔的模块组装与强大的铑催化的[2 + 2 + 2]炔烃环三聚反应相结合，为一组新的高效鳞翅目动物毒素打开了大门，包括首次完整合成鳞翅目细菌素L，M和C 。