Organoboron reagents, such as allyl- and alkylboronic acids, have indisputable value in the applications of synthetic chemistry. The studies presented in this thesis focus on 1,1′-Bi-2-naphthol (BINOL)-catalyzed asymmetric homologation of the boronic acids by trifluoromethylated diazoalkanes to obtain allyl- and alkylboronic acids. 

First, BINOL was used as the organocatalyst for the homologation of vinylboroxines. This novel methodology allowed us to obtain in situ generated chiral allylboronic acids, which were protected by diamino naphthalene (DanH). Then the BDan derivatives were purified by chromatography, and subsequently hydrolyzed to allylboronic acids. In situ generated boronates underwent a one-pot allylboration reaction as well as oxidation to give homoallyl alcohols and α-CF₃-substituted secondary alcohols. 

Next, a method for asymmetric homologation of alkyl- and arylboronic esters was also developed using (R)-iodo-BINOL catalyst and diazoalkane reagents. The method allowed to access in situ generated trifluoromethylated boronic esters which later were derivatized to BDan analogues or converted to alcohols as well as deborylated carboxylates with high enantiopurities. 

Finally, the applicability of the enantioenriched α-CF₃-substituted allylboronic acids was investigated in Cu-catalyzed cross-coupling with α-diazoketones. This method is suitable for the synthesis of alkenyl-trifluoromethyl-substituted alkyl ketones with high selectivity. Using this procedure, the β-fluoride and β-hydride eliminations could be avoided, allowing stereocontrolled construction of new C(sp³)–C(sp³) bonds.