A mild, atom‐economic, and metal‐free α‐C−H amination of ethers using relatively stable nonafluorobutanesulfonyl (nonaflyl, Nf) azide as the aminating reagent to give N‐sulfonyl hemiaminals is reported. This enables unprecedented C(sp3) difunctionalization reactions, leading to diverse functionalized amino group containing compounds starting from simple ethers in one pot.

A new strategy for the synthesis of the oxa-azabicyclo[3.3.1]nonane subunit, a component of the naucleamide E core structure, has been developed. This annulation reaction between 1-substituted 3,4-dihydroisoquinolines and coumarin derivatives conveniently affords the oxa-azabicyclo[3.3.1]nonane framework via a base-mediated cascade cyclization under aqueous conditions. The value of this work lies in the efficient formation of the oxa-azabicyclo[3.3.1]nonane skeleton via a process whereby all the C-C, C-O, and C-N bond formations occur in a single chemical operation. In addition, the subsequent ring opening of these compounds furnished pyridoisoquinoline derivatives.

A mild, atom‐economic, and metal‐free α‐C−H amination of ethers using relatively stable nonafluorobutanesulfonyl (nonaflyl, Nf) azide as the aminating reagent to give N‐sulfonyl hemiaminals is reported. This enables unprecedented C(sp3) difunctionalization reactions, leading to diverse functionalized amino group containing compounds starting from simple ethers in one pot.