This thesis describes the development of a novel organocatalytic method for the synthesis of chiral allyl- and propargyl- organoboron compounds with high enantioselectivity. These organoboron species are versatile building blocks in asymmetric synthesis.

We have developed a new efficient homologation method of alkenyl boronic acids. This reaction affords enantiomerically enriched trifluoromethylated allylboronates. These organoboron species were used in allylboration of carbonyl compounds, imines and indole derivatives. The reactions proceeded with a remarkably high stereoselectivity to give homoallylic alcohols and amines. In addition, the chiral allylboronic acids can be oxidized to the corresponding alcohols with retention of the configuration.

Based on the homologation of alkenylboronic acids a new three-component reaction is developed. This reaction involved coupling of alkynyl boronates, diazo compounds and ketones in the presence of chiral organocatalysts. This coupling proceeds with high selectivity under mild reaction conditions. The three-component coupling reaction is based on a homologation–allylboration sequence. The process is suitable for synthesis of CF₃- and TMS-substituted allenols with excellent diastereo- and enantioselectivity. Application of aromatic, cyclic and non-cyclic ketones leads to formation of chiral tertiary allenols.

We have also studied the effects of boronic acid esters on the outcome of the homologation reaction. It was found that a facile transesterification of the boronate precursors with the organocatalyst, BINOL derivatives, is a prerequisite of the successful homologation reaction.

We have developed a new three-component catalytic coupling reaction of alkynyl boronates, diazomethanes, and aliphatic/aromatic ketones in the presence of BINOL derivatives. The reaction proceeds with a remarkably high enantio- and diastereoselectivity (up to three contiguous stereocenters) affording tertiary CF₃-allenols in a single operational step. The reaction proceeds under mild, neutral, metal-free conditions, which leads to a high level of functional group tolerance.

Chiral α-substituted allylboronic acids were synthesized by asymmetric homologation of alkenylboronic acids using CF3/TMS-diazomethanes in the presence of BINOL catalyst and ethanol. The chiral α-substituted allylboronic acids were reacted with aldehydes or oxidized to alcohols in situ with a high degree of chirality transfer. The oxygen-sensitive allylboronic acids can be purified via their isolated diaminonaphthalene (DanH)-protected derivatives. The highly reactive purified allylboronic acids reacted in a self-catalyzed reaction at room temperature with ketones, imines, and indoles to give congested trifluoromethylated homoallylic alcohols/amines with up to three contiguous stereocenters.

A one-pot approach to fluorinated hydroxamic acid, amide, and thioamide derivatives is reported. The reaction proceeds via an N-perfluoroalkylation of nitrosoarenes with perfluoroalkanesulfinates, resulting in labile N-perfluoroalkylated hydroxylamines. By the addition of suitable additives, a controllable oxy/thiodefluorination of the fluorinated hydroxylamine intermediates was achieved. The method highlights N-perfluoroalkylated amines as versatile intermediates for further synthesis.