Synthesis of polysubstituted arenes through organocatalytic benzannulation

Abstract

Polysubstituted arenes serve as ubiquitous structural cores of aromatic compounds with significant applications in chemistry, biological science, and materials science. Among all the synthetic approaches toward these highly functionalized arenes, organocatalytic benzannulation represents one of the most efficient and versatile transformations in the assembly of structurally diverse arene architectures under mild conditions with exceptional chemo-, regio- or stereoselectivities. Thus, the development of new benzannulation reactions through organocatalysis has attracted much attention in the past ten years. This review systemically presents recent advances in the organocatalytic benzannulation strategies, categorized as follows: (1) Brønsted acid-catalysis, (2) secondary amine catalysis, (3) primary amine catalysis, (4) tertiary amine catalysis, (5) tertiary phosphine catalysis, and (6) N-heterocyclic carbene catalysis. Each part is further classified into several types according to the number of carbon atoms contributed by different synthons participating in the cyclization reaction. The reaction mechanisms involved in different benzannulation strategies were highlighted.