In 2022, Arrayas et. al. elucidated the copper catalyzed anti-hydroboration of alkynes, affording E-alkenyl boronic esters exclusively (Figure ). This transformation, facilitated by Cu(OTf)2.Tol employing a dual ligand system comprising of BINAP and xantphos, demonstrates a strategic implementation of orthogonal reactivity, whereby two in-situ formed copper complexes operate synergistically without negative impacts. The scope of the transformation encompassed a diverse array of propiolate esters and amides as well as analogues of complex molecules affording corresponding alkenyl boronate esters in high yields and E selectivity (Figure ). Systematic investigations revealed that Cu(OTf)2.Tol/xantphos (24.8) was required for the borylation of the alkynes using B2Pin2. On the other hand, fluorescence quenching, transient absorption spectra (TAS), and kinetic studies demonstrated the role of Cu(OTf)2.Tol/BINAP (24.15) as the triplet photosensitizer. While it facilitated the sensitization of both Z and E alkenyl boronic ester through Dexter energy transfer, 148-150 a kinetic selectivity towards sensitization of Z isomers was observed in the excited state (Figure ).