Cycloisomerization of π-Coupled Heteroatom Nucleophiles by Gold Catalysis: En Route to Regiochemically Defined Heterocycles

Abstract

Since the dawn of millennium, catalytic gold chemistry is at the forefront to set off diverse organic reactions via unique activation of π-bonded molecules. Within this purview, cycloisomerization of heteroatom nucleophiles linked to a π-system is one of the well recognized chemistry for the construction of numerous heterocyclic cores. Though the rudimentary aspects of this transformation are reviewed by several groups in different timeline, a holistic view on regiochemistry of such reactions went largely overlooked. Hence, this account emphasizes the gold catalyzed regioselective cycloisomerization of structurally distinctive π-connected hetero-nucleophiles leading to different heterocycles documented in the last two decades. From an application perspective, this account also highlights those methodologies which find a role in the total synthesis of natural products. Wherever appropriate, mechanistic details and contributing factors for selectivity are also discussed.

Keywords: Cycloisomerization; Gold catalysis; Heterocycles; Regioselectivity; π-linked nucleophiles.