Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
Universitat Rovira i Virgili, C/Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.
Angew Chem Int Ed Engl. 2023 Mar 6;62(11):e202217803. doi: 10.1002/anie.202217803. Epub 2023 Feb 1.
A conceptually novel catalytic domino approach is presented for the synthesis of highly functional 1,4-dihydro-2H-1,3-benzoxazine-2-one derivatives. Key to the chemoselectivity is a proper design of the precursor to override thermodynamically favored parasitic cyclization processes and empower the formation of the desired product through Thorpe-Ingold effects. The synthetic diversity of these CO -based heterocycles is further demonstrated, and the isolation of a reaction intermediate supports an unusual ring-expansion sequence from an α-alkylidene, five-membered cyclic carbonate to a six-membered cyclic carbamate by N-induced isomerization.
提出了一种概念新颖的催化多米诺方法，用于合成高度功能化的 1,4-二氢-2H-1,3-苯并恶嗪-2-酮衍生物。关键的选择性是通过适当设计前体来克服热力学上有利的副环化过程，并通过 Thorpe-Ingold 效应来实现所需产物的形成。这些基于 CO 的杂环化合物的合成多样性进一步得到了证明，并且反应中间体的分离支持了通过 N 诱导异构化从α-亚烷基、五元环状碳酸酯到六元环状氨基甲酸酯的不寻常的环扩张序列。
