The article discusses the development of catalytic C–C bond formations using boron-based pronucleophiles, specifically allylic and allenyl boronates or boranes, in conjunction with C(sp³) electrophiles such as O,O-acetals, N,O-aminals, ethers, and carbohydrates. The reactions are most efficiently catalyzed by In(I) triflate. Notably, chiral counteranion-directed, catalytic asymmetric allylation and allenylolation of N,O-aminals were developed using a catalyst system composed of In(I) chloride and a chiral silver 2,2′-dihydroxy-1,1′-binaphthalene (BINOL)-phosphate. The study highlights the unique reactivity and selectivity of these reactions, particularly the α-selectivity observed in the allylation of N,O-aminals. The proposed mechanism involves the generation of a chiral low-oxidation state In species as the active catalyst, leading to the formation of α-selective products. The research represents a significant advancement in the field of asymmetric catalysis and provides a novel approach for the synthesis of complex molecules.The article discusses the development of catalytic C–C bond formations using boron-based pronucleophiles, specifically allylic and allenyl boronates or boranes, in conjunction with C(sp³) electrophiles such as O,O-acetals, N,O-aminals, ethers, and carbohydrates. The reactions are most efficiently catalyzed by In(I) triflate. Notably, chiral counteranion-directed, catalytic asymmetric allylation and allenylolation of N,O-aminals were developed using a catalyst system composed of In(I) chloride and a chiral silver 2,2′-dihydroxy-1,1′-binaphthalene (BINOL)-phosphate. The study highlights the unique reactivity and selectivity of these reactions, particularly the α-selectivity observed in the allylation of N,O-aminals. The proposed mechanism involves the generation of a chiral low-oxidation state In species as the active catalyst, leading to the formation of α-selective products. The research represents a significant advancement in the field of asymmetric catalysis and provides a novel approach for the synthesis of complex molecules.