2,2-dimethyl-3-methylenechroman-4-one | 78115-50-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 2,2-dimethyl-3-methylenechroman-4-one
• 英文别名: 2,2-Dimethyl-3-methylene-4-chromanone；2,2-dimethyl-3-methylidenechromen-4-one
• CAS: 78115-50-1
• 化学式: C₁₂H₁₂O₂
• 分子量: 188.226
• InChiKey: QXXRLLNWJLRDEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  1,3-二苯基异苯并呋喃 、 2,2-dimethyl-3-methylenechroman-4-one 以 二氯甲烷 为溶剂， 反应 72.0h， 以51%的产率得到2',2'-Dimethyl-1,8-diphenylspiro[11-oxatricyclo[6.2.1.02,7]undeca-2,4,6-triene-9,3'-chromene]-4'-one
  参考文献：
  名称：

  Palladium-catalysed cascade molecular queuing-cycloaddition, cyclocondensation and Diels–Alder reactions

  摘要：

  The locked s-cis enone system present in 3-methylenequinol-4-ones and chroman-4-ones offers substantial further synthetic opportunities as illustrated by the ability to function as a 2 pi-component in 1,3-dipolar cycloaddition reactions, or as a 2 pi- or 4 pi-component in Diels-Alder reactions. Cascade molecular queuing-cycloadditions/cyclocondensation are reported. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01177-1
• 作为产物：
  描述：

  2,2-二甲基-苯并二氢吡喃-4-酮 、 四甲基甲烷二胺 在 乙酸酐 作用下， 反应 3.0h， 以8%的产率得到2,2-dimethyl-3-methylenechroman-4-one
  参考文献：
  名称：

  Antimicrobial 3-methylene flavanones

  摘要：

  The antimicrobial activity previously attributed to flavanone Mannich bases was found to be due to their breakdown products, 3-methyleneflavanones. Among the latter compounds, highest potency was observed when the flavanone phenyl ring contained bromine or chlorine substituents. 3-Methylene-2-phenylflavanone (8) was synthesized and shown to be equal to hexachlorophene in tests against representative Gram-positive microorganisms.

  DOI：

  10.1021/jm00141a011

文献信息

• Asymmetric catalytic 1,3-dipolar cycloaddition of α-diazoesters for synthesis of 1-pyrazoline-based spirochromanones and beyond
  作者：Peng Zhao、Zegong Li、Jun He、Xiaohua Liu、Xiaoming Feng

  DOI：10.1007/s11426-021-1027-7

  日期：2021.8

  A highly enantioselective 1,3-dipolar cycloaddition of α-substituted diazoesters with exocyclic enones was achieved with chiral scandium(III)/N, N’-dioxide complex as the catalyst. This protocol provided a facile and efficient route to optically active 1-pyrazoline-based spirochromanones and others with good outcomes (up to 97% yield, 98% ee with >95:5 dr). Moreover, enantioenriched 2-pyrazoline-based

  以手性钪 (III)/ N, N'-二氧化物配合物为催化剂，实现了 α-取代重氮酯与环外烯酮的高度对映选择性 1,3-偶极环加成反应。该协议为光学活性 1-吡唑啉基螺色满酮和其他具有良好结果的化合物（产率高达 97%，98% ee，>95:5 dr）提供了一种简便有效的途径。此外，还可以通过将 α-取代的重氮酯转换为 α-重氮乙酸酯来获得富含对映体的 2-吡唑啉基螺色满酮。还公开了手性基于吡唑啉的螺化合物向螺环丙烷衍生物的进一步具体转化。
• Enantioselective Radical Hydroacylation of α,β-Unsaturated Carbonyl Compounds with Aldehydes by Triplet Excited Anthraquinone
  作者：Yao Luo、Qi Wei、Liangkun Yang、Yuqiao Zhou、Weidi Cao、Zhishan Su、Xiaohua Liu、Xiaoming Feng

  DOI：10.1021/acscatal.2c04047

  日期：2022.10.21

  hydroacylation of α-substituted α,β-unsaturated carbonyl compounds through direct hydrogen atom transfer in the presence of the photocatalyst anthraquinone and chiral N,N′-dioxide/metal complexes. This mild, robust method provided a facile access to a wide array of chiral ketones with α-tertiary stereocenters by using the readily available aldehyde as a hydroacylation reagent. Based on the spectroscopy experiments

  手性酮的合成一直是化学研究的长期焦点。对映选择性自由基加氢酰化作为获得各种手性酮的有用策略，仅限于与 β-取代烯烃的反应，其中通过立体控制的自由基加成到前手性烯烃产生 β-立体中心。在此，我们通过在光催化剂蒽醌和手性N ,'-二氧化物/金属配合物。这种温和、稳健的方法通过使用容易获得的醛作为氢化酰化试剂，提供了一种容易获得具有 α-叔立体中心的手性酮的方法。基于光谱实验和控制实验以及DFT计算，提出了氢原子转移/自由基加成/对映选择性反向氢原子转移序列。
• Asymmetric Hydrogenation by Relay Catalysis with FLPs and CPAs: Stereodivergent Synthesis of 3-Substituted Flavanones
  作者：Jingjing Chen、Wei Meng、Xiangqing Feng、Haifeng Du

  DOI：10.1021/acs.joc.2c01278

  日期：2022.8.5

  To access flavanones bearing two contiguous stereogenic centers, a metal-free asymmetric hydrogenation of racemic 3-alkylidene flavanones has been developed by relay catalysis with achiral FLPs and chiral phosphoric acids, which represents a successful detour for the challenging hydrogenation of 3-substituted flavones. A wide range of trans- and cis-flavanones were obtained in high yields and ≤97%

  为了获得具有两个连续立体中心的黄烷酮，已经通过非手性 FLP 和手性磷酸的中继催化开发了外消旋 3-亚烷基黄烷酮的无金属不对称氢化，这代表了具有挑战性的 3-取代黄酮氢化的成功绕道。以高产率和≤97% ee 获得了范围广泛的反式和顺式黄烷酮。
• Palladium-Catalyzed Carbonylation of <i>o</i>-Iodophenols with Allenes
  作者：Kazumi Okuro、Howard Alper

  DOI：10.1021/jo962283c

  日期：1997.3.1
• Synthesis of quinol-4-ones and chroman-4-ones via a palladium-catalysed cascade carbonylation–allene insertion
  作者：Ronald Grigg、Angela Liu、Duncan Shaw、Selvaratnam Suganthan、Diane E Woodall、Gnanamoly Yoganathan

  DOI：10.1016/s0040-4039(00)01176-x

  日期：2000.9

  Palladium(0)-catalysed termolecular queuing processes involving oxidative addition to aryl iodides followed by low pressure carbonylation, allene insertion and capture of the resulting pi-allyl palladium(II) species by an internal O- or N-nucleophile occur in good yields. One-pot 3-methylene chromanone/quinolone synthesis-Michael addition-stereoselective reduction are also reported. (C) 2000 Elsevier Science Ltd. All rights reserved.