2-cinnamylcycloheptanone

• 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-cinnamylcycloheptanone
• 英文别名: 2-cinnamylcycloheptan-1-one；2-(3-Phenylprop-2-enyl)cycloheptan-1-one；2-(3-phenylprop-2-enyl)cycloheptan-1-one
• 化学式: C₁₆H₂₀O
• 分子量: 228.334
• InChiKey: HIXVHCVJSYJHMA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  烯丙苯 、 环庚酮 在 palladium diacetate 、 三苯基膦 、 对苯醌 、 L-脯氨酸 作用下， 以 甲苯 为溶剂， 反应 10.0h， 以36%的产率得到2-cinnamylcycloheptanone
  参考文献：
  名称：

  Synergistic Pd/Enamine Catalysis: A Strategy for the C–H/C–H Oxidative Coupling of Allylarenes with Unactivated Ketones

  摘要：

  By combining catalytic nucleophilic enamine activation with Pd-catalyzed C-H activation of allylarenes, the first oxidative allylic alkylation of unactivated ketones was achieved. Mechanistically, the Pd-catalyzed allylic C-H activation and proline-catalyzed ketone nucleophilic activation worked synergistically for the oxidative cross-coupling between allylarenes and unactivated ketones.

  DOI：

  10.1021/ol501584d

文献信息

• Palladium-Catalyzed Allylic Alkylation of Simple Ketones with Allylic Alcohols and Its Mechanistic Study
  作者：Xiaohong Huo、Guoqiang Yang、Delong Liu、Yangang Liu、Ilya D. Gridnev、Wanbin Zhang

  DOI：10.1002/anie.201403410

  日期：2014.6.23

  Allylic alcohols were directly used in Pd‐catalyzed allylic alkylations of simple ketones under mild reaction conditions. The reaction proceeded smoothly at 20 °C by the concerted action of a Pd catalyst, a pyrrolidine co‐catalyst, and a hydrogen‐bonding solvent, and does not require any additional reagents. A computational study suggested that methanol plays a crucial role in the formation of the

  在温和的反应条件下，烯丙醇直接用于钯催化的简单酮的烯丙基烷基化反应。在20°C下，Pd催化剂，吡咯烷助催化剂和氢键合溶剂的协同作用使反应顺利进行，不需要任何其他试剂。一项计算研究表明，甲醇通过降低活化势垒在π-烯丙基铝配合物的形成中起着至关重要的作用。
• Dual Palladium- and Proline-Catalyzed Allylic Alkylation of Enolizable Ketones and Aldehydes with Allylic Alcohols
  作者：Ippei Usui、Stefan Schmidt、Bernhard Breit

  DOI：10.1021/ol9001812

  日期：2009.3.19

  The dual Pd/proline-catalyzed α-allylation reaction of a variety of enolizable ketones and aldehydes with allylic alcohols is described. In this reaction, the choice of a large-bite angle ligand Xantphos and proline as the organocatalyst was essential for generation of the crucial π-allyl Pd intermediate from allylic alcohol, followed by nucleophilic attack of the enamine formed in situ from the corresponding

  描述了多种可烯化的酮和醛与烯丙基醇的双重Pd /脯氨酸催化的α-烯丙基化反应。在该反应中，选择大咬角配体Xantphos和脯氨酸作为有机催化剂对于从烯丙醇生成关键的π-烯丙基Pd中间体至关重要，然后由相应的可烯醇化羰基原位形成烯胺进行亲核攻击底物和脯氨酸。
• Cooperative Palladium/Proline-Catalyzed Direct α-Allylic Alkylation of Ketones with Alkynes
  作者：Chi Yang、Kaifan Zhang、Zijun Wu、Hequan Yao、Aijun Lin

  DOI：10.1021/acs.orglett.6b02649

  日期：2016.10.21

  The cooperative palladium/l-proline-catalyzed direct α-allylic alkylation of ketones with alkynes is achieved. This reaction exhibits high atom economy since a leaving group is not liberated and a stoichiometric amount of extra oxidant is not needed. A broad range of functional groups are tolerated, and the reaction scope could be further expanded to aldehydes.

  实现了炔与炔的钯/ 1-脯氨酸协同催化的直接α-烯丙基烷基化。由于不释放离去基团并且不需要化学计量的额外氧化剂，因此该反应具有高原子经济性。可以容忍各种各样的官能团，并且反应范围可以进一步扩大到醛。
• Cooperativity between the Substrate and Ligand in Palladium-Catalyzed Allylic Alkylation Using 1-Aryl-1-propynes
  作者：Aniket Gupta、Anusuya Saha、Ajijur Rahaman、Jogendra Kumar、Eringathodi Suresh、Bishwajit Ganguly、Sukalyan Bhadra

  DOI：10.1021/acs.joc.2c00592

  日期：2022.8.5

  a variety of ketones, β-keto esters, aldehydes, etc., during enamine–palladium catalysis. Density functional theory calculations reveal that Bz-Gly-OH assists in the formation of an enamine that attacks the π-allylpalladium complex via an outer sphere mechanism. The preliminary result points to an asymmetric allylic alkylation under a new mode of bifunctional catalysis.

  在烯胺-钯催化过程中，单保护氨基酸 Bz-Gly-OH 有助于各种酮、β-酮酯、醛等的烯丙基烷基化。密度泛函理论计算表明，Bz-Gly-OH 有助于形成烯胺，该烯胺通过外球机制攻击 π-烯丙基钯络合物。初步结果表明在双功能催化新模式下的不对称烯丙基烷基化。
• Chemo- and Regioselectivity-Tunable Pd-Catalyzed Allylic Alkylation of Imines
  作者：Jian-Ping Chen、Qian Peng、Bai-Lin Lei、Xue-Long Hou、Yun-Dong Wu

  DOI：10.1021/ja2039503

  日期：2011.9.14

  alpha-Carbanions of cyclic and acyclic imines have been successfully applied as nucleophiles in the Pd-catalyzed allylic alkylation reaction. Tuning of chemo- and regioselectivity has been realized by using t-BuOK/THF and LDA/toluene to give branched and linear products, respectively, with high regio- and diastereoselectivities. A plausible mechanism is proposed on the basis of the experimental results and DFT calculations.