Reactivity of tert-butanesulfinamides in palladium-catalyzed allylic substitutions

•Metalated tert-butanesulfinamides are good partners for Pd(0)-catalyzed allylic substitutions.•Allylic substitution of linear allylic carbonates proceeds in the absence of base.•The cross-coupling is totally regioselective and highly diastereoselective.•The sulfur atom remains configurationally stable throughout the allylation process.

The performance of tert-butanesulfinamides as nitrogen nucleophiles in Pd(0)-catalyzed allylic substitution reactions has been investigated. Metalated N-alkyl and N-acetyl sulfinamides have been identified as suitable partners for the reaction with π-allyl–palladium complexes. The cross-coupling of N-acetyl tert-butanesulfinamide with 2- or 3-substituted linear allylic carbonates is achieved in the presence of Pd(OAc)2 (5 mol%) and dppe (7.5 mol%) and does not require an additional base. The reaction proceeds in high yields (59–98%) to produce the corresponding E-configured linear allylic sulfinamides in a totally regioselective and highly diastereoselective manner. The sulfur atom remains configurationally stable throughout the allylation process, and thus the coupling products are obtained in enantiomerically pure form.

Graphical abstractMetalated N-alkyl and N-acetyl tert-butanesulfinamides have been identified as suitable partners for Pd(0)-catalyzed allylic substitution reactions. Significantly, the regio- and diastereoselective cross-coupling of N-acetyl tert-butanesulfinamide with linear allylic 2- or 3-substituted carbonates is achieved with a readily available catalyst and does not require the presence of an added base.Figure optionsDownload full-size imageDownload as PowerPoint slide