Borylative transition metal-free couplings of vinyl iodides with various nucleophiles, alkenes or alkynes

Alkyl boronic esters are highly valuable compounds in organic chemistry and related fields due to their good stability and highly versatile reactivity. In this edge article, stereoselective borylative couplings of vinyl iodides with various nucleophiles, alkenes or alkynes is reported. These coupling reactions proceed through stereospecific hydroboration and subsequent stereospecific 1,2-metallate rearrangement. The cascades utilize readily available reagents and proceed without the need of a transition metal catalyst. The stereoselective synthesis of alkylboronic esters from vinyl iodides and various nucleophiles, alkenes or alkynes is presented. Reactions proceed through hydroborations and 1,2-metallate rearrangements without any transition metal catalyst.