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Silver-Mediated Cascade Synthesis of Functionalized 1,4-Dihydro-2H-benzo-1,3-oxazin-2-ones from Carbon Dioxide |
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| Authors: | Xuetong Li Dr Jordi Benet-Buchholz Dr Eduardo C Escudero-Adán Prof Arjan W Kleij |
| Institution: | 1. 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;2. Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain |
| Abstract: | 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 CO2-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. |
| Keywords: | Carbamates Carbon Dioxide Cascade Reactions Homogeneous Catalysis Silver |