Abstract
This review provides a comprehensive summary of advances in synthetic strategies for structurally complex angular triquinane natural products, with a particular emphasis on terpenoids and alkaloids over the past two decades. The formidable challenge inherent in these frameworks lies in the stereoselective construction of the congested, angularly fused triquinane core bearing one or more quaternary stereocenters. We systematically categorize and critically evaluate the key methodologies employed to construct this central motif, highlighting four major strategic approaches: (i) The Pauson-Khand reaction; (ii) tandem or cascade cyclization processes; (iii) skeletal reorganization strategies; and (iv) other innovative methods, including ring-expansion, radical cyclizations, and photochemical pathways.