C4-arylation and domino C4-arylation/3,2-carbonyl migration of indoles by tuning Pd catalytic modes: Pd(i)-Pd(ii) catalysis Pd(ii) catalysis.

Efficient C4-arylation and domino C4-arylation/3,2-carbonyl migration of indoles have been developed. The former route enables C4-arylation in a highly efficient and mild manner and the latter route provides an alternative straightforward protocol for synthesis of C2/C4 disubstituted indoles. The mechanism studies imply that the different reaction pathways were tuned by the distinct acid additives, which led to either the Pd(i)-Pd(ii) pathway or Pd(ii) catalysis.

A Metal-Free Three-Component Reaction of trans-β-Nitrostyrene Derivatives, Dibromo Amides, and Amines Leading to Functionalized Amidines.

A mild, metal-free, and multicomponent route for the preparation of N-acyl amidines from nitroalkene derivatives, dibromo amides, and amines has been developed that accesses an initial α,α-dibromonitroalkane intermediate that can undergo C-C bond cleavage. This protocol offers an alternative approach toward N-acyl amidines and features the rapid construction of amidine frameworks with high diversity and complexity. The procedure also accesses bisamidine and α,β-unsaturated amidines which are challenging targets by traditional methods.