This study reports the development of catalytic asymmetric C–C bond formations using In(I) as a catalyst, particularly with allylic and allenyl boronates as pronucleophiles. The research highlights the use of In(I) triflate as an efficient catalyst for the allylation and allenylation of various electrophiles, including O,O-acetals and N,O-aminals. The study also demonstrates the effectiveness of In(I) chloride in combination with a chiral silver BINOL-phosphate for asymmetric catalysis. The results show that In(I) is more electron-rich and less Lewis acidic than In(III), making it a better catalyst for these reactions. The study also explores the use of allylic boronates in the formation of C–C bonds with C(sp³) electrophiles such as acetals, aminals, ethers, and carbohydrates. The mechanism proposed involves a transmetalation process, leading to the formation of chiral allylic In(I) species. The study also demonstrates the application of In(I) in asymmetric catalysis, particularly in the allylation of N,O-aminals, achieving high enantioselectivity. The results indicate that In(I) can act as a dual catalyst, activating both the electrophile and the nucleophile. The study concludes that the use of In(I) in catalytic asymmetric C–C bond formations represents a significant advancement in the field of organometallic chemistry.This study reports the development of catalytic asymmetric C–C bond formations using In(I) as a catalyst, particularly with allylic and allenyl boronates as pronucleophiles. The research highlights the use of In(I) triflate as an efficient catalyst for the allylation and allenylation of various electrophiles, including O,O-acetals and N,O-aminals. The study also demonstrates the effectiveness of In(I) chloride in combination with a chiral silver BINOL-phosphate for asymmetric catalysis. The results show that In(I) is more electron-rich and less Lewis acidic than In(III), making it a better catalyst for these reactions. The study also explores the use of allylic boronates in the formation of C–C bonds with C(sp³) electrophiles such as acetals, aminals, ethers, and carbohydrates. The mechanism proposed involves a transmetalation process, leading to the formation of chiral allylic In(I) species. The study also demonstrates the application of In(I) in asymmetric catalysis, particularly in the allylation of N,O-aminals, achieving high enantioselectivity. The results indicate that In(I) can act as a dual catalyst, activating both the electrophile and the nucleophile. The study concludes that the use of In(I) in catalytic asymmetric C–C bond formations represents a significant advancement in the field of organometallic chemistry.