2,2-dimethyl-3-oxo-4-phenylbutanal

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,2-dimethyl-3-oxo-4-phenylbutanal
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: RUDWNUOSXSYKPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-3-oxo-4-phenylbutanal 在 三乙胺 、 三(二甲胺基)膦 作用下， 以 四氢呋喃 为溶剂， 反应 34.33h， 生成 N-(1-benzyl-4,4-difluoro-2,2-dimethylbut-3-en-1-ylidene)-4-methylbenzenesulfonamide
  参考文献：
  名称：

  Nucleophilic 5-endo-trig Cyclization of 3,3-Difluoroallylic Metal Enolates and Enamides: Facile Synthesis of Ring-Fluorinated Dihydroheteroles

  摘要：

  Metal enolates and enamides bearing difluoroallylic moieties underwent nucleophilic 5-endo-trig cyclization, a process considered to be disfavored according to Baldwin's rules. Whereas no C-cyclization was observed in these reactions, O- and N-cyclization proceeded exclusively to afford 5-fluorinated 2-alkylidene-2,3-dihydrofurans and -2,3-dihydropyrroles, respectively.

  DOI：

  10.1055/s-0033-1340857
• 作为产物：
  描述：

  苯乙酰氯 在 正丁基锂 、 草酸 、 二异丙胺 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 15.42h， 生成 2,2-dimethyl-3-oxo-4-phenylbutanal
  参考文献：
  名称：

  Nucleophilic 5-endo-trig Cyclization of 3,3-Difluoroallylic Metal Enolates and Enamides: Facile Synthesis of Ring-Fluorinated Dihydroheteroles

  摘要：

  Metal enolates and enamides bearing difluoroallylic moieties underwent nucleophilic 5-endo-trig cyclization, a process considered to be disfavored according to Baldwin's rules. Whereas no C-cyclization was observed in these reactions, O- and N-cyclization proceeded exclusively to afford 5-fluorinated 2-alkylidene-2,3-dihydrofurans and -2,3-dihydropyrroles, respectively.

  DOI：

  10.1055/s-0033-1340857

文献信息

• Decarboxylative Annulation of α-Amino Acids with β-Ketoaldehydes
  作者：Anirudra Paul、N. R. Thimmegowda、Thiago Galani Cruz、Daniel Seidel

  DOI：10.1021/acs.orglett.7b03721

  日期：2018.2.2

  Indolizidine and quinolizidine derivatives are readily assembled from l-proline or (±)-pipecolic acid and β-ketoaldehydes via a decarboxylative annulation process. These reactions are promoted by acetic acid and involve azomethine ylides as reactive intermediates.

  吲哚里西啶和喹里西啶衍生物很容易由l-脯氨酸或(±)-哌啶酸和β-酮醛通过脱羧成环过程组装而成。这些反应由乙酸促进，并涉及偶氮甲碱叶立德作为反应中间体。
• Diastereoselective SmI₂-Mediated 3-<i>exo</i>-trig Cyclisation of δ-Oxo-Alkylidenemalonates to Cyclopropanols
  作者：Sophie Bezzenine-Lafollée、François Guibé、Riadh Zriba、Marie-George Guillerez

  DOI：10.1055/s-2005-872683

  日期：——

  In the presence of samarium diiodide and a proton donor (tert-butanol or phenol), δ-oxo-γ,γ-disubstituted-alkylidenemalonates readily cyclise according to the 3-exo-trig mode to give, depending on the exact nature of the substrate, trans and cis cyclopropanols or lactones derived from the cis isomers. Total stereoselectivity towards the formation of trans cyclopropanols is observed with di-tert-butyl alkylidenemalonates when PhOH is used as the protonating agent.

  在镧二碘和质子供体（如叔丁醇或酚）的存在下，δ-氧-γ,γ-二取代烯基马来酸酯易于按照3-exo-trig模式环化，生成的产物取决于底物的具体性质，可能是反式和顺式环丙醇或源自顺式异构体的内酯。当使用酚作为质子化剂时，二叔丁基烯基马来酸酯对反式环丙醇的形成表现出完全的立体选择性。
• Nucleophilic 5-endo-trig Cyclization of 3,3-Difluoroallylic Ketone Enolates: Synthesis of 5-Fluorinated 2-Alkylidene-2,3-dihydrofurans
  作者：Junji Ichikawa、Takeshi Fujita、Kotaro Sakoda、Masahiro Ikeda、Masahiro Hattori

  DOI：10.1055/s-0032-1317709

  日期：——

  3,3-Difluoroallylic ketones readily undergo nucleophilic 5-endo-trig cyclization through their metal enolates to afford 5-fluorinated 2-alkylidene-2,3-dihydrofurans. O-Cyclization exclusively occurred via intramolecular substitution of the vinylic fluorines.
• DITGENS, K.;KRAEMER, W.;ELBE, H. -L.
  作者：DITGENS, K.、KRAEMER, W.、ELBE, H. -L.

  DOI：——

  日期：——
• Nucleophilic 5-endo-trig Cyclization of 3,3-Difluoroallylic Metal Enolates and Enamides: Facile Synthesis of Ring-Fluorinated Dihydroheteroles
  作者：Junji Ichikawa、Takeshi Fujita、Masahiro Ikeda、Masahiro Hattori、Kotaro Sakoda

  DOI：10.1055/s-0033-1340857

  日期：——

  Metal enolates and enamides bearing difluoroallylic moieties underwent nucleophilic 5-endo-trig cyclization, a process considered to be disfavored according to Baldwin's rules. Whereas no C-cyclization was observed in these reactions, O- and N-cyclization proceeded exclusively to afford 5-fluorinated 2-alkylidene-2,3-dihydrofurans and -2,3-dihydropyrroles, respectively.