Steric Tuning of Sulfinamide/Sulfoxides as Chiral Ligands with C1, Pseudo-meso, and Pseudo‑C2 Symmetries: Application in Rhodium(I)-Mediated Arylation

Description

A new family of sulfinamide/sulfoxide derivatives was synthesized as chiral bidentate ligands by stereoselective additions of methylsulfinyl carbanions to N-tert-butylsulfinylimines. The new ligands, with C1, pseudo-meso, and pseudo-C2 symmetries, were successfully assayed in Rh-catalyzed additions of arylboronic acids to activated ketones. The sterically dissymmetric C1 ligand (RS,SC,RS)-N-[1-(phenylsulfinyl)-3-methylbut-2-yl] tert-butylsulfinamide turned out to be the optimal one, allowing the 1,4-additions of diverse arylboronic acids, on different α,β-unsaturated cyclic ketones with high chemical yields and enantioselectivities up to >99% ee.

Abstract

Ministerio de Economía y Competitividad (Grant CTQ2016-78580-C2-2R)

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