A method for the synthesis of C3a acetoxy hexahydropyrrolo[2,3-b]indole derivatives via a PhI(OAc)₂/ⁿBu₄NI mediated tandem iodocyclization/acetoxylation has been developed. The newly developed synthetic strategy features the single-step assembly of various C3a acetoxylated tetrahydropyrrole-, tetrahydrofuran-, and lactone-fused indolines under mild reaction conditions, which enabled efficient asymmetric synthesis of (−)-protubonine B.