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Garcia-Ruiz, Cristina; Chen, Jack L.-Y.; Sandford, Christopher; Feeney, Kathryn; Lorenzo, Paula; Berionni, Guillaume; Mayr, Herbert; Aggarwal, Varinder K. (2017): Stereospecific Allylic Functionalization: The Reactions of Allylboronate Complexes with Electrophiles. In: Journal of the American Chemical Society, Vol. 139, No. 43: pp. 15324-15327
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Allylboronic esters react readily with carbonyls and imines (pi-electrophiles), but are unreactive toward a range of other electrophiles. By addition of an aryllithium, the corresponding allylboronate complexes display enhanced nucleophilicity, enabling addition to a range of electrophiles (tropylium, benzodithiolylium, activated pyridines, Eschenmoser's salt, Togni's reagent, Selectfluor, diisopropyl azodicarboxylate (DIAD), MeSX) in high regio- and stereocontrol. This protocol provides access to key new functionalities, including quaternary stereogenic centers bearing moieties such as fluorine and the trifluoromethyl group. The allylboronate complexes were determined to be 7 to 10 orders o f magnitude more reactive than the parent boronic ester.