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.
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