2(3H)-呋喃酮,二氢-4,4-二甲基-3-亚甲基-5-苯基- | 192458-59-6

• 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: 2(3H)-呋喃酮,二氢-4,4-二甲基-3-亚甲基-5-苯基-
• 英文名称: rac-4,4-dimethyl-3-methylene-5-phenyldihydrofuran-2-one
• 英文别名: 4,4-dimethyl-3-methylene-5-phenyl-dihydro-furan-2-one；4,4-Dimethyl-3-methylidene-5-phenyloxolan-2-one；4,4-dimethyl-3-methylidene-5-phenyloxolan-2-one
• CAS: 192458-59-6
• 化学式: C₁₃H₁₄O₂
• 分子量: 202.253
• InChiKey: VWYOGRPDRVRTCD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  methyl 3-hydroxy-3-methyl-2-methylenebutanoate 在 silver-graphite 、 三溴化磷 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 生成 2(3H)-呋喃酮,二氢-4,4-二甲基-3-亚甲基-5-苯基-
  参考文献：
  名称：

  Enantioselective Dreiding-Schmidt reactions: asymmetric synthesis and analysis of α-methylene-γ-butyrolactones

  摘要：

  The zinc/silver-graphite mediated Dreiding-Schmidt reactions between aldehydes and the 2-bromomethyl-acrylate derived sultamamides (+)/(-)-28 or (+)/(-)-30 gave the corresponding substituted alpha-methylene-gamma-butyrolactones with ee's up to 90%. Enantiomerically pure compounds were obtained by semipreparative HPLC using a chiral stationary phase. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00166-3

文献信息

• Lewis Acid Catalyzed Allylboration:  Discovery, Optimization, and Application to the Formation of Stereogenic Quaternary Carbon Centers
  作者：Jason W. J. Kennedy、Dennis G. Hall

  DOI：10.1021/jo049773m

  日期：2004.6.1

  A full account of the development of the first catalytic manifold for the additions of allylboronates to aldehydes is described. The thermal additions (both diastereospecific and enantioselective) of 2-carboxyester 3,3-disubstituted allylboronates 1 to both aromatic and aliphatic aldehydes give biologically and synthetically important exo-methylene butyrolactones 2 containing a β-quaternary carbon

  描述了将烯丙基硼酸酯加成到醛中的第一催化歧管的发展的完整说明。将2-羧酸酯3,3-二取代的烯丙基硼酸酯1热加成（非对映体特异性和对映体选择性）对芳香族和脂肪族醛均具有生物学和合成意义的外亚甲基丁内酯2包含一个β-季碳中心。尽管热反应在室温下需要14 d才能完成，但是某些金属盐的存在可以使反应12-16 h，同时保留未催化过程中观察到的非对映特异性。描述了对催化作用起源的初步机理研究，以及内酯2立体选择性转化为环状和非环状的立体三单元体，具有潜在的合成中间体用途。
• Brønsted Acid-Catalyzed Allylboration:  Short and Stereodivergent Synthesis of All Four Eupomatilone Diastereomers with Crystallographic Assignments
  作者：Siu Hong Yu、Michael J. Ferguson、Robert McDonald、Dennis G. Hall

  DOI：10.1021/ja054171l

  日期：2005.9.1

  structures brings an end to the ambiguity of the original stereochemical assignments. Further to the TfOH-catalyzed allylboration, the synthetic route featured a number of remarkable observations: the surprising reactivity of 2-bromo-3,4,5-trimethoxybenzaldehyde, the subtle reagent control observed in the hydrogenation of an alpha-exo-methylene lactone intermediate, and the success of a difficult case of

  本研究描述了一种新的 Brønsted 酸催化烯丙基硼酸化方法，适用于最困难的、电子失活的烯丙基硼酸酯和醛底物。该方法避免使用金属离子，而是使用简单且廉价的催化剂三氟甲磺酸。它作为一种互补的烯丙基硼化变体的有用性通过四步、立体发散合成从单一烯丙基硼酸酯中合成 eupomatilone-6 的所有四种非对映异构体。多达五个 X 射线晶体结构支持的立体化学的彻底证明结束了原始立体化学分配的模糊性。除了 TfOH 催化的烯丙基硼化反应之外，该合成路线还具有许多值得注意的观察结果：2-溴-3,4,5-三甲氧基苯甲醛的惊人反应性，
• Triflic Acid-Catalyzed Additions of 2-Alkoxycarbonyl Allylboronates to Aldehydes. Study of Scope and Mechanistic Investigation of the Reaction Stereochemistry
  作者：Tim G. Elford、Yuichiro Arimura、Siu Hong Yu、Dennis G. Hall

  DOI：10.1021/jo062151b

  日期：2007.2.1

  The substrate scope and the effect of substrate on the observed inversion of stereoselectivity in the triflic acid-catalyzed allylboration reaction between 2-alkoxycarbonyl allylboronates and aldehydes are presented. A mechanistic investigation is described so as to confirm the involvement of a carbocation intermediate as the source of stereochemical inversion. This methodology allows a facile access

  介绍了底物的范围和底物对在三氟乙酸催化的2-硼氧基羰基烯丙基硼酸酯和醛之间的三氟甲磺酸催化的烯丙基硼化反应中观察到的立体选择性转化的影响。描述了一种机理研究，以确认碳正离子中间体作为立体化学转化的来源。该方法允许容易地获得在α位具有外亚甲基的β，γ-二取代的五元环内酯。
• Enantioselective Dreiding-Schmidt reactions: asymmetric synthesis and analysis of α-methylene-γ-butyrolactones
  作者：René Csuk、Christina Schröder、Sonja Hutter、Kristina Mohr

  DOI：10.1016/s0957-4166(97)00166-3

  日期：1997.5

  The zinc/silver-graphite mediated Dreiding-Schmidt reactions between aldehydes and the 2-bromomethyl-acrylate derived sultamamides (+)/(-)-28 or (+)/(-)-30 gave the corresponding substituted alpha-methylene-gamma-butyrolactones with ee's up to 90%. Enantiomerically pure compounds were obtained by semipreparative HPLC using a chiral stationary phase. (C) 1997 Elsevier Science Ltd.