3-acetyl-5,5-diisopropyldihydro-2(3H)-furanone | 127236-68-4

• 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: 3-acetyl-5,5-diisopropyldihydro-2(3H)-furanone
• 英文别名: 3-Acetyl-5,5-di(propan-2-yl)oxolan-2-one
• CAS: 127236-68-4
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: AUZAQDZTTCBDCV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  2,3,4-三甲基-3-戊醇 在 dirhodium tetraacetate 甲烷磺酰基叠氮化物 作用下， 生成 3-acetyl-5,5-diisopropyldihydro-2(3H)-furanone
  参考文献：
  名称：

  在羧酸铑（II）和铑（II）羧酰胺催化的重氮酯的分子内类胡萝卜素碳氢插入中高选择性合成γ-内酯

  摘要：

  乙酸铑（II）和铑（II）乙酰胺催化的重氮酯分解形成γ-内酯，产率高，区域选择性和非对映选择性高。

  DOI：

  10.1016/s0040-4039(01)93408-2

文献信息

• 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.
• Electronic Effects in Dirhodium(II) Carboxylates. Linear Free Energy Relationships in Catalyzed Decompositions of Diazo Compounds and CO and Isonitrile Complexation
  作者：Michael C. Pirrung、Andrew T. Morehead

  DOI：10.1021/ja00099a017

  日期：1994.10

  A linear free energy analysis of substituent effects in rhodium carboxylate complexes has been conducted. Two reactions of diazo compounds involving intramolecular competition between (1) O-ylide formation and secondary C-H insertion, and (2) tertiary C-H and primary C-H insertion were studied as well as complexation effects on the IR frequencies of CO and tert-butyl isocyanide. Aliphatic and aromatic carboxylate complexes were included. Regression equations that describe these processes include contributions from sigma(alpha) (polarizability) and sigma(F) (field effects) and, for the benzoates, sigma(R) (resonance). Complexes that deviate from the LFER include rhodium trifluoroacetate and rhodium triptycenecarboxylate, and their behavior was explained through (partial) release of the free carbene. The effect of ligand polarizability on selectivity in these reactions was interpreted as evidence for the importance of backbonding from rhodium to the carbene carbon in the product-determining step. The ability of these complexes to backbond was shown through the complexation study. Higher selectivity with increasing ability to backbond is analogous to other carbenes such as difluorocarbene. Increased selectivity engendered by backbonding could occur by facilitating the reversal of an intermediate complex between the carbenoid and the C-H bond undergoing insertion. Increased selectivity engendered by field effects and polarizability could be explained by increased selectivity for electron-rich sites.
• DOYLE, MICHAEL P.;BAGHERI, VAHID;PEARSON, MATTHEW M.;EDWARDS, JOHN D., TETRAHEDRON LETT., 30,(1989) N0, C. 7001-7004
  作者：DOYLE, MICHAEL P.、BAGHERI, VAHID、PEARSON, MATTHEW M.、EDWARDS, JOHN D.

  DOI：——

  日期：——
• Highly selective γ-lactone syntheses by intramolecular carbenoid carbon-hydrogen insertion in rhodium(II) carboxylate and rhodium(II) carboxamide catalyzed reactions of diazo esters
  作者：Michael P. Doyle、Vahid Bagheri、Matthew M. Pearson、John D. Edwards

  DOI：10.1016/s0040-4039(01)93408-2

  日期：——

  Rhodium(II) acetate and rhodium(II) acetamide catalyzed decomposition of diazo esters forms γ-lactones in high yield and with exceptionally high regio- and diastereoselectivity.

  乙酸铑（II）和铑（II）乙酰胺催化的重氮酯分解形成γ-内酯，产率高，区域选择性和非对映选择性高。