Ikonnikova Viktoria A, Cheibas Cristina, Gayraud Oscar, Bosnidou Alexandra E, Casaretto Nicolas, Frison Gilles, Nay Bastien
Laboratoire de Synthèse Organique, Ecole Polytechnique, CNRS, ENSTA, Institut Polytechnique de Paris, F-91128 Palaiseau, France.
Laboratoire de Chimie Moléculaire, Ecole Polytechnique, CNRS, Institut Polytechnique de Paris, F-91128 Palaiseau, France.
Beilstein J Org Chem. 2024 Jan 25;20:162-169. doi: 10.3762/bjoc.20.15. eCollection 2024.
The Hock cleavage, which is compatible with tandem processes, was applied to the synthesis of 1-aryltetralines through a one-pot transformation from readily available benzyl(prenyl)malonate substrates. After the photooxygenation of the prenyl moiety, the resulting hydroperoxide was directly engaged in a Hock cleavage by adding a Lewis acid. The presence of an aromatic nucleophile in the reaction mixture and that of a benzyl moiety on the substrate resulted in tandem Friedel-Crafts reactions to form the 1-aryltetraline products. These compounds share a close analogy to the cyclolignan natural products. Experimental observations and a DFT study support the involvement of an aldehyde intermediate during the Friedel-Crafts reactions, rather than an oxocarbenium.
与串联反应兼容的霍克裂解反应，通过一锅法将易得的苄基（异戊烯基）丙二酸酯底物转化，应用于1-芳基四氢萘的合成。异戊烯基部分经光氧化后，通过加入路易斯酸使生成的氢过氧化物直接进行霍克裂解反应。反应混合物中存在芳族亲核试剂以及底物上存在苄基部分，导致串联傅克反应形成1-芳基四氢萘产物。这些化合物与环木脂素天然产物极为相似。实验观察结果和密度泛函理论研究支持在傅克反应过程中涉及醛中间体，而非氧鎓碳正离子。
