Enantioselective Sequential Catalytic Arylation‐Fukuyama Cross‐coupling of 1,1‐Biszincioalkane Linchpins

Federico Banchini (1) , Baptiste Leroux (2) , Erwan Le Gall (2) , Marc Presset (2) , Olivier Jackowski (1) , Fabrice Chemla (3, 1) , Alejandro Perez‐luna (1)

1 IPCM - Institut Parisien de Chimie Moléculaire
2 ICMPE - Institut de Chimie et des Matériaux Paris-Est
3 SU - Sorbonne Université

1,1‐Bis(iodozincio)alkanes are used as dinucleophilic linchpins in an enantioselective double cross‐coupling reaction sequence involving aryl iodides and then thioesters. The two catalytic C−C bond‐forming reactions are achieved in the same pot through two distinct palladium‐based catalytic systems: a first non‐enantioselective one delivering configurationally labile secondary benzylzinc species from an achiral precursor, and a second enantioconvergent one that operates a highly efficient dynamic kinetic resolution of the racemic intermediates. This strategy, new in the area of asymmetric synthesis through two consecutive electrophilic substitution reactions of geminated C(sp 3 )‐organodimetallics, provides useful methodology to access in a modular fashion acyclic α ‐disubstituted ketone products with very high enantiomeric purity.

Domaines: Chimie

Federico Banchini, Baptiste Leroux, Erwan Le Gall, Marc Presset, Olivier Jackowski, et al.. Enantioselective Sequential Catalytic Arylation‐Fukuyama Cross‐coupling of 1,1‐Biszincioalkane Linchpins. Chemistry - A European Journal, 2023, 29 (36), pp.e202301084. ⟨10.1002/chem.202301084⟩. ⟨hal-04197445⟩