Stereoselective synthesis of hexahydroindoles and octahydrocyclohepta[b]pyrroles via gold(I)-catalyzed intramolecular 1,4-hydroamination of cyclic 1,3-dienes

The gold(I)-catalyzed intramolecular hydroamination of cyclohexa-1,3-dienes bearing an arylsulfonamide at the C-5 position proceeds in a 1,4-addition manner to afford hexahydroindole derivatives in a diastereoselective fashion and in good yields, whereas octahydrocyclohepta[b]pyrrole derivatives can be obtained from seven-membered ring substrates under the same reaction conditions. Coordination of the gold(I) species to the 1,3-diene at the double bond adjacent to the arylsulfonamide tether gave an η2-alkene gold complex. The anti-attack of the sulfonamide to the η2-alkene gold complex at the terminal position of the 1,3-diene resulted in the formation of the fused bicyclic ring with a newly formed Au–C bond at the allylic position. Allylic rearrangement of the η1-allylgold complex followed by protodemetalation provided the fused heterobicyclic skeletons and regenerated the catalyst.

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