3-(p-tolyl)cyclobut-2-en-1-one | 1383658-28-3

• 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: 3-(p-tolyl)cyclobut-2-en-1-one
• 英文别名: 3-(4-Methylphenyl)-2-cyclobuten-1-one；3-(4-methylphenyl)cyclobut-2-en-1-one
• CAS: 1383658-28-3
• 化学式: C₁₁H₁₀O
• 分子量: 158.2
• InChiKey: FUKFVOUTWGIQLC-UHFFFAOYSA-N

物化性质

• 沸点：
  263.4±30.0 °C(Predicted)
• 密度：
  1.136±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(p-tolyl)cyclobut-2-en-1-one 在 吡啶 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 8.75h， 生成 Ethyl 4-(4-methylphenyl)-6-oxo-1,7-dihydrodiazepine-7-carboxylate
  参考文献：
  名称：

  Efficient Approach to 1,2-Diazepines via Formal Diazomethylene Insertion into the C–C bond of Cyclobutenones

  摘要：

  Efficient monocyclic 1,2-diazepine formation via a tandem electrocyclization reaction of cyclobutenones with lithiodiazoacetate is demonstrated. The reaction proceeds through an oxy anion-accelerated 4 pi-ring opening of cyclobutene followed by an 8 pi-ring closure of the resultant oxy anion-substituted diazo-diene under mild conditions to furnish a 1,2-diazepine via formal diazomethylene insertion into the C-C bond of cyclobutenone.

  DOI：

  10.1021/ol301474g
• 作为产物：
  描述：

  1-(2,2-二溴乙烯)-4-甲基苯 在 正丁基锂 、 四甲基乙二胺 、 溶剂黄146 、 锌 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙醚 、 乙醇 、 正己烷 为溶剂， 反应 8.5h， 生成 3-(p-tolyl)cyclobut-2-en-1-one
  参考文献：
  名称：

  Efficient Approach to 1,2-Diazepines via Formal Diazomethylene Insertion into the C–C bond of Cyclobutenones

  摘要：

  Efficient monocyclic 1,2-diazepine formation via a tandem electrocyclization reaction of cyclobutenones with lithiodiazoacetate is demonstrated. The reaction proceeds through an oxy anion-accelerated 4 pi-ring opening of cyclobutene followed by an 8 pi-ring closure of the resultant oxy anion-substituted diazo-diene under mild conditions to furnish a 1,2-diazepine via formal diazomethylene insertion into the C-C bond of cyclobutenone.

  DOI：

  10.1021/ol301474g

文献信息

• Synthesis of Silylated Cyclobutanone and Cyclobutene Derivatives Involving 1,4‐Addition of Zinc‐Based Silicon Nucleophiles
  作者：Ming Cui、Martin Oestreich

  DOI：10.1002/chem.202102993

  日期：2021.11.22

  intermediate metal enolate can be trapped as an enol phosphate and further reacted with Grignard reagents in Kumada cross-coupling reactions. By this, a range of silylated cyclobutanone and cyclobutene derivatives becomes accessible.

  一系列高度取代的环丁烯酮与锌基亲核试剂进行 1,4-加成反应，对于无位阻受体，无需铜催化剂的帮助。中间体金属烯醇化物可以作为烯醇磷酸盐被捕获，并在 Kumada 交叉偶联反应中进一步与格氏试剂反应。由此，可以获得一系列甲硅烷基化环丁酮和环丁烯衍生物。
• Asymmetric Catalytic Diverse Ring Opening/Cycloadditions of Cyclobutenones with (<i>E</i>)-Alkenyloxindoles and (<i>E</i>)-Dioxopyrrolidines
  作者：Yao Luo、Hang Zhang、Siyuan Wang、Yuqiao Zhou、Shunxi Dong、Xiaoming Feng

  DOI：10.1021/acs.orglett.0c00608

  日期：2020.4.3

  Highly enantioselective ring-opening/cycloaddition reactions of cyclobutenones were achieved by employing chiral N,N′-dioxide/metal complexes as the catalysts. The Diels–Alder type cycloaddition with (E)-alkenyloxindoles yielded spirocyclohexaneoxindoles with excellent results. Meanwhile, a hetero-Diels–Alder process occurred with (E)-dioxopyrrolidines to afford spiropyrrolidinone-dihydropyranone derivatives

  环丁烯酮的高度对映选择性开环/环加成反应是通过使用手性N，N'-二氧化物/金属络合物作为催化剂来实现的。用（E）-烯基氧吲哚进行的Diels-Alder型环加成反应生成的螺环己烷氧吲哚具有优异的效果。同时，与（E）-二氧杂吡咯烷类发生异Diels-Alder过程，得到螺吡咯烷酮-二氢吡喃酮衍生物。
• Acetonitrile Activation: An Effective Two‐Carbon Unit for Cyclization
  作者：Qixue Qin、Xiao Luo、Jialiang Wei、Yuchao Zhu、Xiaojin Wen、Song Song、Ning Jiao

  DOI：10.1002/anie.201900947

  日期：2019.3.22

  two‐carbon (C2) cyclization building block. The present protocol successfully inhibits the competitive cycloaddition with the C≡N bond of acetonitrile, but enables the in situ formation of an unsaturated carbon–carbon bond and the subsequent cycloaddition as a C2 unit. This chemistry features simple reaction conditions, high chemoselectivities, wide substrate scope, and offers a new and practical approach

  开发了一种新的乙腈活化方法，用于通过[2 + 2]环化作用构建环丁烯酮。乙腈首次被用作双碳（C2）环化的基础材料。本方案成功地抑制了乙腈C≡N键的竞争性环加成反应，但能够原位形成不饱和碳-碳键并随后将环加成反应作为C2单元。该化学方法具有反应条件简单，化学选择性高，底物范围广的特点，并为环丁烯酮和环丁烯亚胺提供了一种新的实用方法。
• Enantioselective Synthesis of 3‐Substituted Cyclobutenes by Catalytic Conjugate Addition/Trapping Strategies
  作者：Changxu Zhong、Yingchao Huang、Haocheng Zhang、Qiang Zhou、Yu Liu、Ping Lu

  DOI：10.1002/anie.201913825

  日期：2020.2.10

  A copper-catalyzed tandem process to generate chiral cyclobutene derivatives has been developed. It is based on an enantioselective conjugate addition or reduction of a cyclobutenone and sequential trapping with a chlorophosphate in a one-pot process. These phosphates are stable under mildly acidic conditions and serve as good electrophiles in Negishi coupling reactions.

  已经开发了铜催化的串联方法以产生手性环丁烯衍生物。它基于一锅法中环丁烯酮的对映选择性共轭添加或还原，以及用氯磷酸盐顺序捕集。这些磷酸盐在弱酸性条件下稳定，在Negishi偶联反应中可作为良好的亲电子试剂。
• [4+3]-Cycloaddition Reaction of Sulfilimines with Cyclobutenones: Access to Benzazepinones
  作者：Xiaozhou Xie、Jiangtao Sun

  DOI：10.1021/acs.orglett.1c03413

  日期：2021.11.19

  A catalyst-free [4+3]-cycloaddition reaction of N-aryl sulfilimines with cyclobutenones is described, which provides a straightforward protocol for synthesizing 1,5-dihydro-2H-benzo[b]azepin-2-ones under mild reaction conditions. This reaction features a broad substrate scope and good functional group tolerance and does not require catalysts or additives. Moreover, using N-pyridinyl sulfilimine as

  描述了N-芳基硫亚胺与环丁烯酮的无催化剂 [4+3] -环加成反应，为在温和反应下合成 1,5-二氢-2 H-苯并 [ b ]azepin-2-ones提供了一个简单的方案状况。该反应具有广泛的底物范围和良好的官能团耐受性，并且不需要催化剂或添加剂。此外，以N-吡啶基硫亚胺为底物，还制备了一系列吡啶并氮杂酮类化合物。