The robust nature of this three-component APBM reaction was demonstrated by the successful synthesis of approximately 70 amines (Figure , Panels A-C). The applicability of this method was initially assessed with diverse boronic reagents, coupled with compounds 22 and 23 (Figure , Panel A). A variety of alkyl boronic reagents, such as primary (25), cyclic (28, 30, 31) branched alkyls (38), and tertiary (29), were seamlessly integrated with high yields. Interestingly, compound 30 was obtained with identical yield under standard conditions in the absence of light, indicating irradiation is not prerequisite for every substrate (See Supporting Information for details). The reaction also demonstrated excellent functional group tolerance. Boronic species with ether (32), sulfide (33), halide (33), pyrazole (34), free alcohol (35), ketone (36), olefin (37), and ester (38) were all compatible with this transformation, giving the corresponding amines with moderate to good yields. Benzene isosters, such as bicyclo[1.1.1]pentane (39), adamantane (40) could also be efficiently installed, which can potentially providing an approach for rapid scaffold hopping of bioactive phenyl amines synthesized with classic PBM reaction using phenyl boronic acids. Sterically hindered quaternary carbons and architecturally complex structures, often incorporated in bioactive small molecules to enhance potency, selectivity, and metabolic stability through enriching three-dimensionality 4 , were also addressed. Utilizing tertiary trifluoroborate salts, primarily accessed through our hydrazone coupling route , we were able to synthesize corresponding alkyl amines containing a quaternary center with C(sp 3 )-rich chains tethered with diverse functional scaffolds. These include tetrahydropyran (41), linear and cyclic amines (42, 44), terminal alkyne (43), heteroaromatics (45-47), and anisole (48), showcasing significant tolerance of steric hindrance around the boron center.