Indium-catalyzed annulation of 2-aryl- and 2-heteroarylindoles with propargyl ethers: concise synthesis and photophysical properties of diverse aryl- and heteroaryl-annulated[a]carbazoles.

Treatment of 2-aryl- and 2-heteroarylindoles with propargyl ethers in the presence of a catalytic amount of indium nonafluorobutanesulfonate [In(ONf)(3)] gave aryl- and heteroaryl-annulated[a]carbazoles in good yields. The synthetically attractive feature is reflected by its applicability to a wide range of 2-aryl- and 2-heteroarylindoles. In the annulation reaction, propargyl ethers act as C3 sources (HC[triple bond]C-CH(2)OR). Among these, two carbon atoms are incorporated into the product as members of a newly constructed aromatic ring and the remaining carbon atom forms a methyl group on the aromatic ring, where the methyl group is always located next to the C3 position of the indole nucleus. The methyl group can be easily removed through SeO(2) oxidation followed by decarbonylation with RhCl(CO)(PPh(3))(2)-Ph(2)P(CH(2))(3)PPh(2) as a catalyst. The new annulation strategy is applicable also to symmetrical dimers such as bithiophene and bifuran derivatives. Mechanistic studies suggest that the first step is addition reaction initiated by regioselective nucleophilic attack of the C3 of 2-aryl- and 2-heteroarylindoles to the internal carbon atom of the C[triple bond]C bond in propargyl ethers. The next stage is ring-closing S(N)2 process kicking out the alkoxy group and then aromatization via a 1,3-hydrogen shift is the final step. The two carbon-carbon bond-forming reactions achieved in one-pot contribute largely to the reduction in the number of steps for the synthesis of aryl- and heteroaryl-annulated[a]carbazoles. Furthermore, utilization of the Fischer indole synthesis for efficient supply of the substrates, 2-aryl- and 2-heteroarylindoles, is another important factor shortening the overall process. The development of the annulation with a wide substrate scope provided a unique opportunity to evaluate photophysical properties of a series of aryl- and heteroaryl-annulated[a]carbazoles. Almost all the compounds evaluated in this study were found to emit purple to green light in the visible region. Some interesting structure-property correlations are also described.