Catalytic Asymmetric Conjugate Reduction

Catalytic asymmetric conjugate boration of α,β-unsaturated sulfones.

The α,β-unsaturated sulfones are suitable activated olefins in catalytic asymmetric conjugate β-boration. These substrates undergo smooth conjugate addition of bis(pinacolato)diboron [B(2)(pin)(2)] catalyzed by nonracemic Cu(I)-diphosphine complexes to provide, upon subsequent oxidation, β-hydroxy sulfones in good yields and high enantiocontrol.

Catalytic asymmetric conjugate addition/oxidative dearomatization towards multifunctional spirocyclic compounds.

Phosphoramidites: marvellous ligands in catalytic asymmetric conjugate addition.

The development of an efficient catalytic system for enantioselective carbon-carbon bond formation by 1,4-addition of organometallic reagents (organolithium, Grignard, and organozinc reagents) to enones is a major challenge in organic synthesis. This Account presents the breakthrough realized in this field using chiral phosphoramidite ligands for copper-catalyzed dialkylzinc additions. Applicat...

Catalytic asymmetric conjugate addition of Grignard reagents to chromones.

A highly regio- and enantioselective copper catalysed direct conjugate addition of Grignard reagents to chromones has been developed taking advantage of the reduced reactivity of the resulting magnesium enolates. This methodology tolerates a broad scope of alkyl Grignards including secondary alkyl magnesium reagents as well as functionalised chromones.

Catalytic asymmetric conjugate addition of terminal alkynes to β-trifluoromethyl α,β-enones.

The first enantioselective conjugate alkynylation of β-trifluoromethyl α,β-enones using terminal alkynes and a taniaphos-Cu(I) complex as catalyst is described. Ketones bearing a trifluoromethylated propargylic chiral centre in the β-position were obtained with good yields and high enantiomeric excesses (up to 99%).