Transition metal catalyzed cross-coupling with excellent control of reactivity and selectivity has been a longstanding subject of research in synthetic organic chemistry.Development of sterically hindered, functionalized, and asymmetric cross-couplings is of importance for rapid construction of complex natural products and drugs.Yet this remains a significant challenge.Our group have set up a program in addressing these issues by designing and developing a series of sterically bulky and conformational rigid phosphorus ligands.1 By employing these ligands, we have successfully achieved sterically demanding aryl-aryl couplings,2aa-c aryl-isopropyl coupling,2d asymmetric biaryl coupling,2e-f and asymmetric dearomatic cross-couplings.2g The methodologies have enabled efficient syntheses of several biaryl natural products, terpenes, and alkaloids.