A copper-catalyzed borylation of allylic nitroalkanes is reported. The method, which exploits the high versatility of the nitroalkane precursors, tolerates a variety of functional groups and allows a straightforward access to diversely substituted allylboronic esters in high yields. This unprecedented reactivity towards copper complexes has been further exploited in the synthesis of a number of γ fluoroallyl boronic esters starting from readily available α fluoroallyl nitroalkanes, as well as in various post-functionalizations towards synthetically useful building blocks. Both the reaction mechanism and the chemoselectivity have been rationalized experimentally and through DFT calculations.
The Supporting Information contains details of DFT protocols, synthetic procedures and characterization data