β-trideuterio-propiophenone | 119458-35-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: β-trideuterio-propiophenone
• 英文别名: propiophenone-d₃；Deuterio-propiophenon-β-D3；3,3,3-trideuterio-1-phenyl-propan-1-one；3,3,3-trideuterio-1-phenylpropan-1-one
• CAS: 119458-35-4
• 化学式: C₉H₁₀O
• 分子量: 137.154
• InChiKey: KRIOVPPHQSLHCZ-FIBGUPNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.28
• 重原子数：
  10.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  β-trideuterio-propiophenone 在 silica-supported ZnCl2 (30%) 、 copper(l) iodide 、 四(三苯基膦)钯 、 C₄₀H₄₈Cl₂FeN₂ 作用下， 以 四氢呋喃 、 2-甲基四氢呋喃 、 1,2-二氯乙烷 为溶剂， 反应 19.1h， 生成
  参考文献：
  名称：

  Iron‐Catalyzed Allylic C(sp3)−H Silylation: Spin‐Crossover‐Efficiency‐Determined Chemoselectivity

  摘要：

  The nuanced role of spin effects remains a critical gap in designing proficient open‐shell catalysts. This study elucidates an iron‐catalyzed allylic C(sp3)−H silylation/alkyne hydrosilylation reaction, in which the spin state of the open‐shell iron catalyst dictates the reaction kinetics and pathway. Specifically, spin crossover led to alkyne hydrosilylation, whereas spin conservation resulted in a novel allylic C(sp3)−H silylation reaction. This chemoselectivity, governed by the spin‐crossover efficiency, reveals an unexpected dimension in spin effects and a first in the realm of transition‐metal‐catalyzed in situ silylation of allylic C(sp3)−H bonds, which had been previously inhibited by the heightened reactivity of alkenes in hydrosilylation reactions. Furthermore, this spin crossover can either accelerate or hinder the reaction at different stages within a single catalytic reaction, a phenomenon scarcely documented. Moreover, we identify a substrate‐assisted C−H activation mechanism, a departure from known ligand‐assisted processes, offering a fresh perspective on C−H activation strategies.

  DOI：

  10.1002/anie.202402044
• 作为产物：
  描述：

  2-benzoyl-3,3,3-trideuteriopropanoic acid 生成 β-trideuterio-propiophenone
  参考文献：
  名称：

  KLUGER R.; BRANDL M., J. ORG. CHEM., 51,(1986) N 21, 3964-3968

  摘要：

  DOI：

文献信息

• Evidence that the availability of an allylic hydrogen governs the regioselectivity of the Wacker oxidation
  作者：Matthew J. Gaunt、Jinquan Yu、Jonathan B. Spencer

  DOI：10.1039/b103066n

  日期：——

  The allylic hydrogen is found to have a dramatic effect on the regioselectivity of the Wacker oxidation, leading to the postulation that an agostic hydrogen or enyl (σ + π) complex helps to stabilise the key intermediate.

  经发现，烯丙氢对Wacker氧化反应的区域选择性产生了显著影响，这导致了一种假设：即松散氢化合物或烯（σ + π）配合物有助于稳定关键中间体。
• Brønsted Acid Catalyzed Friedel–Crafts‐Type Coupling and Dedinitrogenation Reactions of Vinyldiazo Compounds
  作者：Haifeng Zheng、Kuiyong Dong、Daniel Wherritt、Hadi Arman、Michael P. Doyle

  DOI：10.1002/anie.202004328

  日期：2020.8.3

  The direct Friedel–Crafts‐type coupling and dedinitrogenation reactions of vinyldiazo compounds with aromatic compounds using a metal‐free strategy are described. This Brønsted acid catalyzed method is efficient for the formation of α‐diazo β‐carbocations (vinyldiazonium ions), vinyl carbocations, and allylic or homoallylic carbocation species via vinyldiazo compounds. By choosing suitable nucleophilic

  描述了使用无金属策略将乙烯基重氮化合物与芳族化合物进行直接的Friedel-Crafts型偶联和脱二氮反应。这种布朗斯台德酸催化方法可有效地通过乙烯基重氮化合物形成α-重氮β-碳化（乙烯基重氮离子），乙烯基碳正离子以及烯丙基或均烯丙基碳正离子物种。通过选择合适的亲核试剂来选择性地捕获这些中间体，可以获得高至高收率和高选择性的三取代α，β-不饱和酯，β-吲哚取代的重氮酯和二烯。实验洞察力暗示了一种反应机理，涉及乙烯基重氮化合物的选择性质子化和随后释放的二氮形成形成经历分子内1,3-和1的乙烯基阳离子的反应机理。
• Pd-Catalyzed C-H Olefination of (Hetero)Arenes by Using Saturated Ketones as an Olefin Source
  作者：Yaping Shang、Xiaoming Jie、Jun Zhou、Peng Hu、Shijun Huang、Weiping Su

  DOI：10.1002/anie.201208627

  日期：2013.1.21

  Tolerant: By using Pd(OAc)2/PCy3 as a catalyst, both electron‐rich aromatic heterocycles and electron‐deficient fluorobenzenes undergo the dehydrogenative cross‐coupling with (hetero)aryl ethyl ketones in good yields. A broad range of functional groups is tolerated, thus providing a general method for the facile syntheses of chalcones or heterocyclic chalcone analogues. Furthermore, dialkyl ketones can also

  耐受性：通过使用Pd（OAc）2 / PCy 3作为催化剂，富含电子的芳族杂环和缺乏电子的氟苯都可以与（杂）芳基乙基酮进行脱氢交叉偶联，收率很高。宽泛的官能团是可以容忍的，因此提供了一种轻松合成查耳酮或杂环查耳酮类似物的通用方法。此外，二烷基酮也可以参与该转化。
• MIURA, YUJI;HAYASHIDA, KOHKICHI;CHISHIMA, SUSUMU;YOSHIKAWA, MASAYOSHI;TAK+, J. LABELL. COMPOUNDS AND RADIOPHARM., 25,(1988) N 10, C. 1061-1072
  作者：MIURA, YUJI、HAYASHIDA, KOHKICHI、CHISHIMA, SUSUMU、YOSHIKAWA, MASAYOSHI、TAK+

  DOI：——

  日期：——