Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, 215123, Suzhou, Jiangsu, China.
State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, 300071, Tianjin, China.
Nat Commun. 2020 Feb 3;11(1):672. doi: 10.1038/s41467-020-14435-5.
The C-C σ-bond activation of unstrained cycloketones represents an ingenious and advanced technique in synthetic chemistry, but it remains a challenging area which has been largely underexplored. Herein we report an efficient strategy for the direct C-C cleavage of cyclohexanones and cyclopentanones. The cyclic C-C σ-bond is readily cleaved under mild conditions with the aid of an in situ formed side-chain aryl radical. Density functional theory calculations are carried out to shed light on the unusual regioselectivity of C-C bond cleavage. The reaction affords a variety of structurally diverse 3-coumaranones and indanones that widely exist in natural products and bioactive molecules, illustrating the synthetic value of this method.
未受应变的环酮的 C-C σ 键活化是合成化学中一种巧妙且先进的技术，但它仍是一个很大程度上尚未被充分探索的具有挑战性的领域。在此，我们报告了一种用于环己酮和环戊酮的直接 C-C 断裂的有效策略。在温和条件下，借助原位形成的侧链芳基自由基，环状 C-C σ 键可轻易地被切断。密度泛函理论计算阐明了 C-C 键断裂的异常区域选择性。该反应提供了广泛存在于天然产物和生物活性分子中的各种结构多样的 3-色满酮和茚满酮，展示了该方法的合成价值。
