Stereospecific Allylic Functionalization: The Reactions of Allylboronate Complexes with Electrophiles

Cristina García-Ruiz, Jack L.Y. Chen, Christopher Sandford, Kathryn Feeney, Paula Lorenzo, Guillaume Berionni, Herbert Mayr, Varinder K. Aggarwal

Research output: Contribution to journalArticle

Abstract

Allylboronic esters react readily with carbonyls and imines (π-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 of magnitude more reactive than the parent boronic ester.

Original languageEnglish
Pages (from-to)15324-15327
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number43
DOIs
Publication statusPublished - 1 Nov 2017
Externally publishedYes

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    García-Ruiz, C., Chen, J. L. Y., Sandford, C., Feeney, K., Lorenzo, P., Berionni, G., Mayr, H., & Aggarwal, V. K. (2017). Stereospecific Allylic Functionalization: The Reactions of Allylboronate Complexes with Electrophiles. Journal of the American Chemical Society, 139(43), 15324-15327. https://doi.org/10.1021/jacs.7b10240