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ABSTRACT

Various multicyclic heterocycles were synthesized via “rollover” as the key pathway using a Rh(III) catalyst with a catalytic amount of sodium pivalate or copper(II) acetate. 3-Alkynyl-2-heteroarylpyridines were transformed into tri- or tetracyclic heterocycles containing two heteroatoms via an intramolecular alkyne insertion. 3-Aryloyl-2-arylpyridines were derived into 4-azafluoren-9-ols via the intramolecular carbonyl insertion.