Department of Organic Synthesis & Process Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad, 500007, India.
Academy of Scientific and Innovative Research, Ghaziabad, 201002, India.
Angew Chem Int Ed Engl. 2023 Mar 13;62(12):e202215825. doi: 10.1002/anie.202215825. Epub 2023 Feb 9.
The C-H functionalization strategy provides access to valuable molecules that previously required convoluted synthetic attempts. Dual C-H unsymmetrical functionalization, with a single bifunctional reagent, is an effective tactic. Propargyl alcohols (PAs), despite containing a reactive C≡C bond, have not been explored as building blocks via oxidative cleavage. Annulations via C-H activation are a versatile and synthetically attractive strategy. We disclose PA as a new bifunctional reagent for unsymmetrical dual C-H functionalization of biphenylamine for regioselectively annulated outcomes. On tuning the conditions, the annulation bifurcated towards an unusual dual oxidative cyclization. This method accommodates a wide range of PAs and showcases late-stage diversification of some natural products.
C-H 键功能化策略提供了一种获得有价值分子的途径，而这些分子以前需要复杂的合成尝试。使用单个双功能试剂进行双 C-H 不对称功能化是一种有效的策略。尽管炔丙醇 (PAs) 含有反应性 C≡C 键，但它们并未作为构建块通过氧化裂解进行探索。通过 C-H 活化进行环化反应是一种多功能且具有吸引力的合成策略。我们发现 PA 是一种新型双功能试剂，可用于联苯胺的不对称双 C-H 官能化，以获得区域选择性的环化产物。通过调整条件，环化反应发生了分叉，形成了一种不寻常的双重氧化环化。该方法适用于广泛的 PAs，并展示了一些天然产物的后期多样化。
