Cu(I)-diamine complexes were found to catalyse the trifluoromethylation of aryl iodides. In the presence of a small amount of CuX (X = Cl, Br, I) and 1,10-phenanthroline (phen), the cross-coupling reactions of iodoarenes with trifluoromethylsilanes proceeded smoothly to afford trifluoromethylated aromatics in good yields.

Starting from a readily available fluoral derivative, catalytic aromatic trifluoromethylation has been successfully achieved. A small amount of copper(I) iodide-phenanthroline complex catalyzed the cross-coupling reactions of aryl/heteroaryl iodides with the O-silylated hemiaminal of fluoral (trifluoroacetaldehyde) to provide trifluoromethylated arenes in moderate to high yields.

The structural motifs of trifluoromethylated aromatics (Ar‐CF3) have been widely employed in various industrial fields. The high lipophilicity, strong electron‐withdrawing ability, and characteristic size of the trifluoromethyl group is a key influence in the design of pharmaceuticals, agrochemicals, dyes, liquid crystals, and polymers. Therefore, a great deal of attention has been paid to convenient protocols of introducing trifluoromethyl groups into aromatic rings. With respect to the high regiochemical fidelity in aromatic substitution, the cross‐coupling of aryl halides with CF3Cu is one of the most powerful and versatile methods to construct trifluoromethylated aromatics.

A novel method is reported for the synthesis of 9,9-disubstituted 9H-pyrrolo[1,2-a]indoles. Cyclization of 1-[2-(1-aryl(or methyl)ethenyl)phenyl]-1H-pyrroles, which can be easily prepared from 2-(1-aryl(or methyl)ethenyl)anilines, proceeds smoothly, in general, at 08 in the presence of a catalytic (or an equimolar) amount of HI in MeCN to provide the desired products.Introduction. -9H-Pyrrolo[1,2-a]indoles have attracted much attention due to their structural resemblance to cytostatic mytomycine derivatives [1]. Although a number of methods for the preparation of 9H-pyrrolo[1,2-a]indoles have recently been published [2], there have been only few reports on the synthesis of 9,9-disubstituted derivatives [1a] [3]. For example, Cartoon and Cheeseman have reported a synthesis 9,9-diphenyl-9H-pyrrolo[1,2-a]indole by the reaction of 1-(2-lithiophenyl)-1H-pyrrole with benzophenone, followed by acid-catalyzed cyclization of the resulting adducts [3]. Therefore, we embarked upon development of a convenient method for their preparation. In this article, we report that the hydriodic acid-catalyzed (or mediated) cyclization of 1-[2-(1-aryl(or methyl)ethenyl)phenyl]-1H-pyrroles 2 offers an efficient method for the preparation of 9,9-disubstituted 9H-pyrrolo[1,2-a]indoles 3.

Synthesis of 4-Aryl-4-methyl-and 4,4-Dimethyl-4H-pyrrolo[2,1-c][1,4]benzothiazines by an Easy Five-Step SequenceStarting from 2-Sulfanylbenzenamines. -Precursor (XII) is prepared analogously to (VII) following the sequence A)-D). The final cyclization is achieved in the presence of catalytic HI. -(KOBAYASHI*, K.; HYOTA, A.; KONDO, H.; IMAOKA, A.; Synthesis 2012, 19, 3019-3026, http://dx.doi.org/10.1055/s0032-1316769 ; Dep. Chem. Biotechnol., Grad. Sch. Eng., Tottori Univ., Koyama, Tottori 680, Japan; Eng.) -Mais 04-131