We have developed an efficient formylation of pyrroloisoquinolines using bromoisobutyrate and dimethyl sulfoxide as carbonyl reagent. Various formylated pyrroloisoquinolines could be prepared in good yields (up to 94%). This formylation process can be easily scaled up to gram scale with good yield. In most cases of pyrroloisoquinolines without methoxy groups, the combination of bromoisobutyrate and dimethyl sulfoxide could act as a bromination reagent, delivering brominated pyrroloisoquinolines in acceptable to good yields (up to 82%).

We have developed an iron(III) chloride hexahydrate catalyzed formal [3 + 2] cycloaddition of tetrahydroisoquinolines with amide group-bearing Morita-Baylis-Hillman (MBH) carbonates. A range of highly functionalized dihydro-pyrrolo[2,1-a]isoquinolines could be prepared through SN2'/ oxidation/electrocyclization/aromatization cascade (32-62% yield).

<p>We have developed an iron(III) chloride hexahydrate catalyzed formal [3+2] cycloaddition of tetrahydroisoquinolines with amide group-bearing Morita-Baylis-Hillman (MBH) carbonates. A range of highly functionalized dihydropyrrolo[2,1-<i>a</i>]isoquinolines could be prepared through SN2’/oxidation/ electrocyclization/aromatization cascade (32-62% yield).</p><p><br></p>