The present book describes a one-pot, TBA-HS catalyzed method for the synthesis of benzopyran-fused pyranopyrazoles via a domino Knoevenagel hetero Diels–Alder (DKHDA) reaction of some olefin-ether-tethered aldehyde substrates with pyrazolones as an active methylene unit. The aldehyde substrates were obtained by allylating or prenylating 5-aryldiazenylaldehydes. The stereochemistry of all the compounds was confirmed by various 2D NMR experiments; DQF-COSY and NOESY, and single crystal X-Ray diffraction analysis. The entire synthesized compound also screened for their antimicrobial, antituberculosis and antioxidant properties. It is hoped that post-graduate and Ph.D. students will find this book more useful in their research work.