Direct Substitution of Primary Allylic Amines with Sulfinate Salts

Citations Over TimeTop 10% of 2012 papers

Abstract

The NH(2) group in primary allylic amines was substituted directly by sulfinate salts with excellent regio- and stereoselectivities. In the presence of 0.1 mol % [Pd(allyl)Cl](2), 0.4 mol % 1,4-bis(diphenylphosphino)butane (dppb), and excess boric acid, a range of α-unbranched primary allylic amines were smoothly substituted with sodium sulfinates in an α-selective fashion to give structurally diverse allylic sulfones in good to excellent yields with exclusive E selectivity. Replacing dppb with 1,1'-bi-2-naphthol (BINOL) allowed unsymmetric α-chiral primary allylic amines to be transformed into the corresponding allylic sulfones in good to excellent yields with excellent retention of ee. Importantly, the reaction complements known asymmetric methods in substrate scope via its unique ability to provide α-chiral allylic sulfones with high optical purity starting from unsymmetric allylic electrophiles.

Related Papers

• → Development of Versatile Sulfone Electrophiles for Suzuki–Miyaura Cross-Coupling Reactions(2016)93 cited
• → Allylic Phosphates and Allylic Phosphinates as Electrophiles in Efficient Silylcupration Reactions of Acetylenes(2002)37 cited
• → Efficient Activation of Allylic Alcohols in Pd-Catalyzed Allylic Substitution Reactions(2020)18 cited
• → Nickel-Catalyzed Cross-Electrophile Coupling Reactions between Allylic Acetates and gem-Difluorovinyl Tosylate(2022)8 cited
• → ChemInform Abstract: Iron‐Catalyzed Allylic Substitution Reactions of Allylic Ethers with Grignard Reagents.(2016)