The synthesis of organoboron compounds have attracted the attention of the synthetic community. In particular, molecules with C(sp2)‐B bonds enable the transformation to new C−C or C‐heteroatom bonds by well‐established methodologies. Alkenyl boronates have the possibility for further conversion of the boron moiety or functionalization of the double bond. This review gives an overview on the recent methodologies for the selective preparation of the challenging highly substituted alkenyl boronates from alkynes.

A simple and rapid protocol for the anti-Markovnikov hydroboration of alkynes assisted by microwave irradiation has been developed. Pinacolborane smoothly reacts with terminal alkynes to obtain (E)-alkenyl boronates in good yields and short [a] microwave irradiation gave a 25 % yield after 20 minutes (entry 6). Finally, the reaction time was optimized to 18 minutes, leading to a 79 % yield of (E)-styryl pinacolboronate in 4.5 mmol scale (entry 7). [22] Eur.

A copper-catalyzed enantioselective cyclopropanation involving trifluorodiazoethane in the presence of alkenyl boronates has been developed. This transformation enables the preparation of 2-substituted-3-(trifluoromethyl)cyclopropylboronates with high levels of stereocontrol. The products are valuable synthetic intermediates by transformation of the boronate group. This methodology can be applied to the synthesis of novel trifluoromethylated analogues of trans -2-arylcyclopropylamines, which are prevalent motifs in biologically active compounds.