Chiral α-substituted allylboronic acids were synthesized by asymmetric homologation of alkenylboronic acids using CF 3 /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.

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.