trans-3-acetyl-4,5-dihydro-4-phenylfuran-2-(3H)-one | 71870-65-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: trans-3-acetyl-4,5-dihydro-4-phenylfuran-2-(3H)-one
• 英文别名: trans-3-acetyl-4-phenyldihydrofuran-2-one；trans-3-acetyl-4-phenyldihydro-2(3H)-furanone；(3R,4R)-3-acetyl-4-phenyloxolan-2-one
• CAS: 71870-65-0
• 化学式: C₁₂H₁₂O₃
• 分子量: 204.225
• InChiKey: NPIXHGFEXUYLIU-QWRGUYRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-phenylethyl acetoacetate 在 dirhodium tetraacetate 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 乙腈 、 苯 为溶剂， 反应 7.5h， 生成 trans-3-acetyl-4,5-dihydro-4-phenylfuran-2-(3H)-one
  参考文献：
  名称：

  Electronic and steric control in carbon-hydrogen insertion reactions of diazoacetoacetates catalyzed by dirhodium(II) carboxylates and carboxamides

  摘要：

  Carboxylate and carboxamide ligands on dirhodium(II) catalysts can provide enormous regiocontrol in carbon-hydrogen insertion reactions of diazoacetate esters. Whereas 2,3,4-trimethyl-3-pentyl diazoacetoacetate (1) forms gamma-lactone products from insertion into primary and tertiary C-H bonds in a statistical distribution (61:39) with dirhodium(II) tetrakis(perfluorobutyrate), only tertiary C-H insertion is observed with dirhodium(II) tetraacetamide. Similar results are obtained with 2-methyl-2-octyl diazoacetoacetate (3), where competition for insertion exists between secondary and primary C-H bonds and electronic factors govern regioselection. However, with 2-methyl-3-isopropyl-3-heptyl diazoacetoacetate (2) and 2-methyl-1-phenyl-2-propyl diazoacetoacetate (4), product distributions from C-H insertion are invariant with the dirhodium(II) ligands; insertion into a secondary C-H bond is favored over tertiary C-H insertion with 2 (95:5), and insertion into a primary C-H bond is preferred to benzylic secondary C-H insertion with 4 (70:30). In such cases, which are amenable to analyses by MM2 calculations, regioselectivity is determined by conformational preferences for which C-H insertion selectivity can be as random as that found with 2 and 4. When only one C-H bond site is available for insertion to form a five-membered ring product, only one gamma-lactone is observed from reactions catalyzed by dirhodium(II) tetraacetate, and that product is not necessarily the one predicted by presumed electronic preferences.

  DOI：

  10.1021/ja00056a021

文献信息

• Carbenoid Reactions in Rhodium(II)-Catalyzed Decomposition of Iodonium Ylides
  作者：Paul Müller、Daniel Fernandez

  DOI：10.1002/hlca.19950780417

  日期：1995.6.28

  intermediacy of metallocarbenes in decomposition reactions of iodonium ylides with [Rh2(OAc)4] was established by comparison with reactions of the corresponding diazo compounds. The sensitivity of the RhII-catalyzed intermolecular cyclopropane formation from substituted styrenes and bis(methoxycarbonyl)(phenyliodono)methanide (1a) or dimethyl diazomalonate (1b) is identical. The Hammett plot (with σ+)

  通过与相应的重氮化合物的反应进行比较，确定了碘化亚烷基碘与[Rh 2（OAc）4 ]的分解反应中金属卡宾的中间体。由取代的苯乙烯和双（甲氧基羰基）（苯基碘基）甲烷（1a）或重氮丙二酸二甲酯（1b）形成的Rh II催化的分子间环丙烷的敏感性相同。的哈米特图（与σ +）具有-0.47的斜率。碘鎓碘化物和重氮化合物在[Rh 2（OAc）4]催化的环丙烷形成，环加成反应和分子内CH插入，并且在分子内竞争中对环丙烷形成和插入表现出相同的选择性。当在手性催化剂（[Rh 2 （-）-（（S）-ptpa} 4 ]）的存在下进行时，叶立德20c的分子内CH插入导致形成ee为67％的21a，与用重氮化合物20b得到的ee相同。
• α-Amino-α-vinyl-γ-butyrolactone Derivatives from α-{[(Trimethylsilyl)methyl]alkylidene}-γ-butyrolactones
  作者：Marinella Capuzzi、Augusto Gambacorta、Tecla Gasperi、M. Antonietta Loreto、P. Antonio Tardella

  DOI：10.1002/ejoc.200600540

  日期：2006.11

  novel silylated α-ylidene-γ-butyrolactones 2, through ring opening of the intermediate aziridine and loss of the trimethylsilyl group. The stereoselective synthesis of compounds 2, by cross-coupling reactions between α-[(triflyloxy)ylidene]-γ-butyrolactones 3 and tris[(trimethylsilyl)methyl]aluminum, is also described. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

  N-受保护的 α-氨基-α-乙烯基-γ-丁内酯 1 是通过 NsONHCO2Et 与新型甲硅烷基化 α-亚基-γ-丁内酯 2 的氮杂迈克尔型加成获得的，通过中间体氮丙啶的开环和失去三甲基甲硅烷基。还描述了通过 α-[(三氟甲氧基) 亚基]-γ-丁内酯 3 和三 [(三甲基甲硅烷基) 甲基] 铝之间的交叉偶联反应立体选择性合成化​​合物 2。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• REITZ D. B., J. ORG. CHEM., 1979, 44, NO 25, 4707-4709
  作者：REITZ D. B.

  DOI：——

  日期：——
• Electronic and steric control in carbon-hydrogen insertion reactions of diazoacetoacetates catalyzed by dirhodium(II) carboxylates and carboxamides
  作者：Michael P. Doyle、Larry J. Westrum、Wendelmoed N. E. Wolthuis、Marjorie M. See、William P. Boone、Vahid Bagheri、Matthew M. Pearson

  DOI：10.1021/ja00056a021

  日期：1993.2

  Carboxylate and carboxamide ligands on dirhodium(II) catalysts can provide enormous regiocontrol in carbon-hydrogen insertion reactions of diazoacetate esters. Whereas 2,3,4-trimethyl-3-pentyl diazoacetoacetate (1) forms gamma-lactone products from insertion into primary and tertiary C-H bonds in a statistical distribution (61:39) with dirhodium(II) tetrakis(perfluorobutyrate), only tertiary C-H insertion is observed with dirhodium(II) tetraacetamide. Similar results are obtained with 2-methyl-2-octyl diazoacetoacetate (3), where competition for insertion exists between secondary and primary C-H bonds and electronic factors govern regioselection. However, with 2-methyl-3-isopropyl-3-heptyl diazoacetoacetate (2) and 2-methyl-1-phenyl-2-propyl diazoacetoacetate (4), product distributions from C-H insertion are invariant with the dirhodium(II) ligands; insertion into a secondary C-H bond is favored over tertiary C-H insertion with 2 (95:5), and insertion into a primary C-H bond is preferred to benzylic secondary C-H insertion with 4 (70:30). In such cases, which are amenable to analyses by MM2 calculations, regioselectivity is determined by conformational preferences for which C-H insertion selectivity can be as random as that found with 2 and 4. When only one C-H bond site is available for insertion to form a five-membered ring product, only one gamma-lactone is observed from reactions catalyzed by dirhodium(II) tetraacetate, and that product is not necessarily the one predicted by presumed electronic preferences.