Abstract

AbstractAn energy economical and radical‐involved regioselective difunctionalization annulation of 1,6‐enynes with thiosulfonates or selenosulfonates accessing to pyrrolidine derivatives has been developed. The catalytic amount of TBHP was sufficient to initiate and enable the simultaneous formation of a C(sp3)−S(O2Ar) bond and a C(sp2)−S(Ar) or C(sp2)−Se(Ph) bond across the C=C and C≡C bond of 1,6‐enynes by utilizing two different sulphur radicals. The reaction shows broad substrate scope, moderate to good yields, and 100 % atom economy.

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