AbstractIntramolecular cyclization of 1,1‐diaryl‐2,2‐dicyanoethenes promoted by samarium metal in DMF in the presence of TMSCl allowed direct construction of the indene core, whereas 1‐alkyl‐1‐aryl‐2,2‐dicyanoethenes underwent intermolecular coupling cyclization and decyanation under the same conditions. Simultaneously, disilylation occurred at the amino moiety resulting from the reduction of the cyano group. However, only simple reduction of the C=C bonds is observed when a trace amount of water presented.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)