Synthesis of Bis(indolyl)methanes Using Hyper-Cross-Linked Polyaromatic Spheres Decorated with Bromomethyl Groups as Efficient and Recyclable Catalysts.

Highly uniform and hyper-cross-linked polyphenanthrene and polypyrene microspheres were synthesized by Friedel-Crafts bromomethylation of phenanthrene (Phn) and pyrene (Py) in the presence of zinc bromide as a catalyst, followed by self-polymerization of bromomethylated Phn and Py. The resultant 3-D carbon microspheres consisting of micro-, meso-, and macropores bear peripheral unreacted bromomethyl groups, which are directly utilized as catalysts to efficiently promote the electrophilic substitution reaction of indoles with aldehydes to yield a variety of bis(indolyl)methanes. The important features of this catalysis are easy catalyst synthesis, high product yields, environmental benignity, short reaction time, broad substrate scope, use of nontoxic solvents, and recyclability.