6-甲基-3-亚甲基-5-苯基四氢吡喃-2-酮 | 86953-54-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 中文名称: 6-甲基-3-亚甲基-5-苯基四氢吡喃-2-酮
• 英文名称: 6-Methyl-3-methylene-2-oxotetrahydro-2H-pyran
• 英文别名: 6-methyl-3-methylene-5-phenyltetrahydropyran-2-one；6-methyl-3-methylenetetrahydro-2H-pyran-2one；α-Methylen-γ-methyl-δ-valerolacton；6-Methyl-3-methylideneoxan-2-one
• CAS: 86953-54-0
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: DATNGOMRPQIXLJ-UHFFFAOYSA-N

物化性质

• 沸点：
  236.6±19.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  6-甲基-3-亚甲基-5-苯基四氢吡喃-2-酮 在 second-generation metathesis catalyst titanium(IV) isopropylate 、 戊烯 作用下， 以 氘代甲苯 为溶剂， 反应 8.0h， 以100%的产率得到2,5-二甲基-2,3-二氢吡喃-6-酮
  参考文献：
  名称：

  Cross Metathesis of α-Methylene Lactones II:  γ- and δ-Lactones

  摘要：

  The cross metathesis reactivities of alpha-methylene-gamma-butyrolactone and an alpha-methylene-delta-lactone have been investigated. alpha-Methylene-gamma-butyrolactone undergoes rapid and efficient olefin isomerization in the presence of second-generation metathesis catalysts. However, cross metathesis can be achieved with the additive 2,6-dichlorobenzoquinone. In contrast, the alpha-methylene-delta-lactone neither isomerizes nor couples under similar conditions.

  DOI：

  10.1021/ol070574+
• 作为产物：
  描述：

  丁位己内酯 在 sodium tetrahydroborate 、 sodium hydride 作用下， 生成 6-甲基-3-亚甲基-5-苯基四氢吡喃-2-酮
  参考文献：
  名称：

  Thiophosphates and Selenophosphates in Organic Synthesis. A New Approach to Exocyclic Olefins and Bicyclic Enones

  摘要：

  DOI：

  10.1080/10426509608046285

文献信息

• Self-catalytic Michael reaction of enolizable carbonyl compounds. A facile route to α-methylene-δ-valerolactones
  作者：Henryk Krawczyk、Marcin Śliwiński

  DOI：10.1016/j.tet.2003.09.039

  日期：2003.11

  2-phosphono-5-oxoalkanoates 3 were prepared by the Michael reaction of enolizable carbonyl compounds with the acrylate 1. The corresponding 2-phosphono-5-oxoalkanoic acids 4 were converted into α-phosphono-δ-valerolactones 6. The products were shown to be useful substrates for the synthesis of α-methylene-δ-valerolactones 7 by the Horner–Wadsworth–Emmons reaction.

  各种二环己基-2-膦-5- oxoalkanoates 3是由可烯醇化羰基的化合物与丙烯酸酯的迈克尔加成反应来制备1。相应的2-膦酰基-5-氧代链烷酸4被转化为α-膦酰基-δ-戊内酯6。该产品被证明是通过Horner-Wadsworth-Emmons反应合成α-亚甲基-δ-戊内酯7的有用底物。
• Lewis-Base-Catalyzed Reductive Aldol Reaction To Access Quaternary Carbons
  作者：Yvonne C. DePorre、James R. Annand、Sukanta Bar、Corinna S. Schindler

  DOI：10.1021/acs.orglett.8b00507

  日期：2018.5.4

  transformation relies on an electronically differentiated Lewis base catalyst, which is uniquely capable of promoting a reductive aldol reaction of α,α-disubstituted and α,α,β-trisubstituted enones. This approach provides a valuable synthetic alternative for carbon–carbon bond formation in complex molecular settings due to its orthogonal reactivity compared to that of traditional aldol reactions. Based on this

  描述了有效构建带有α-季碳中心的β-羟基内酯和内酰胺的合成方法。该转化依赖于电子分化的路易斯碱催化剂，该催化剂独特地能够促进α，α-二取代的烯醇和α，α，β-三取代的烯酮的还原性羟醛反应。与传统的醛醇缩合反应相比，这种方法具有正交反应性，因此为复杂分子设置中的碳-碳键形成提供了一种有价值的合成方法。基于本文所述的方法，带有α-季碳中心的内酯，内酰胺和吗啉酰胺的产率可达85％和50：1 dr。
• Systematic Investigation into the Matsuda–Heck Reaction of α-Methylene Lactones: How Conformational Constraints Direct the β-H-Elimination Step
  作者：Bernd Schmidt、Felix Wolf、Christopher Ehlert

  DOI：10.1021/acs.joc.6b02207

  日期：2016.11.18

  were correlated with the dihedral angles between Pd and endo-β-H. This correlation revealed that in the case of the six-membered lactone an energetically favorable conformer adopts a nearly synperiplanar Pd/endo-β-H arrangement, whereas for the analogous Pd σ-complex of the five-membered lactone the smallest Pd/endo-β-H dihedral angle is observed for a conformer with a comparatively high potential energy

  α-亚甲基-γ-丁内酯和α-亚甲基-δ-戊内酯与芳烃重氮盐在Pd催化的Matsuda-Heck偶联作用下分别与α-苄基丁烯化物或戊烯醇化物或与α-苄基内酯结合。观察到的区域选择性强烈依赖于环的大小，六元环仅产生α-苄基戊烯醚化物，而五元α-亚甲基内酯与具有高比例（E）-α-亚苄基-γ-的区域异构体混合物反应丁内酯。DFT计算表明，这些差异的原因不是热力学而是动力学性质。插入Pd-芳基键所产生的Pdσ-复合物构象的相对能量与Pd和内在分子之间的二面角相关-β-H。这种相关性表明，在六元内酯的情况下，在能量上有利的构象异构体采用接近同平面的Pd /内-β-H排列，而对于五元内酯的类似Pdσ-复合物，最小的Pd /内-对于具有相对高的势能的构象异构体，观察到β-H二面角。exo-亚甲基内酯的Matsuda-Heck芳基化反应的优化条件最终被用于天然产物anemarcoumarin A的合成。
• Modulators of cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions, methods of treatment, and process for making the modulators
  申请人：Vertex Pharmaceuticals Incorporated

  公开号：US11066417B2

  公开（公告）日：2021-07-20

  Compounds of Formula (I): pharmaceutically acceptable salts thereof, deuterated derivatives of any of the foregoing, and metabolites of any of the foregoing are disclosed. Pharmaceutical compositions comprising the same, methods of treating cystic fibrosis using the same, and methods for making the same are also disclosed.

  式 (I) 的化合物： 公开了前述化合物的药学上可接受的盐、前述化合物的氚代衍生物以及前述化合物的代谢物。还公开了包含上述物质的药物组合物、使用上述物质治疗囊性纤维化的方法以及上述物质的制造方法。
• Palladium-catalyzed carbonylation. A new synthesis of .alpha.-methylene .gamma.-, .delta.-, .epsilon.-lactams and lactones including bicyclic lactams of pyrrolizidine and indolizidine skeletons
  作者：Miwako Mori、Yumiko Washioka、Takao Urayama、Kagari Yoshiura、Katsumi Chiba、Yoshio Ban

  DOI：10.1021/jo00170a037

  日期：1983.11