We report herein a new method for the synthesis of densely functionalized chiral allyl SCF , SCF R, SCN and SAr species with a separate CF functionality. The synthetic approach is based on selenium-catalyzed sulfenofunctionalization of chiral α-CF allylboronic acids. The reactions proceeded with remarkably high stereo-, diastereo- and site-selectivity, based on the formation of a stable thiiranium ion followed by rapid deborylative ring opening.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9828052PMC
http://dx.doi.org/10.1002/anie.202210509DOI Listing

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We report herein a new method for the synthesis of densely functionalized chiral allyl SCF , SCF R, SCN and SAr species with a separate CF functionality. The synthetic approach is based on selenium-catalyzed sulfenofunctionalization of chiral α-CF allylboronic acids. The reactions proceeded with remarkably high stereo-, diastereo- and site-selectivity, based on the formation of a stable thiiranium ion followed by rapid deborylative ring opening.

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Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances.

Angew Chem Int Ed Engl

November 2020

Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois, 61801, USA.

The last decade has witnessed a burgeoning of new methods for the enantioselective vicinal difunctionalization of alkenes initiated by electrophilic sulfenyl group transfer. The addition of sulfenium ions to alkenes results in the generation of chiral, non-racemic thiiranium ions. These highly reactive intermediates are susceptible to attack by a myriad of nucleophiles in a stereospecific ring-opening event to afford anti 1,2-sulfenofunctionalized products.

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