This guide is based on the synthesis of bisquinlone based phosphine ligands and desulfitative carbon-carbon bond forming reactions. It is divided into 3 chapters which include first an overview about heterocyclic BINAP analogues. In this chapter, survey of developing atropisomeric biheteroaryl backbone-containing bisphosphines, their designing concept, synthetic approaches and some of their important applications are discussed. Second, efficient synthesis of functionalized novel bisquinolone based mono- and diphosphine ligands of the aza-BINAP type. Preliminary studies confirm that these novel types of aza-BINAP phosphines containing an enamide moiety incorporated into the heteroaryl ring are indeed useful ligands in transition metal-catalyzed transformations. Third, palladium(0)- catalyzed, copper(I)-mediated desulfitative C–C cross-coupling protocol (Liebeskind–Srogl type) of cyclic thioamides and thioureas with alkenylboronic acids, vinyl- and (het)arylstannanes, and arylsiloxanes is performed. These C–C cross-couplings are a valuable extension of the traditional Liebeskind–Srogl reactions utilizing thioethers as electrophilic reagents.