An asymmetric Heck reaction allows desymmetrization of substituted cyclic olefins in high dr and ee. A bisphosphine oxide is uniquely stereoselective for this purpose. Desymmetrization of bicyclic olefins via hydroarylation can also be realized in high ee.

BACKGROUND Tandem olefin metathesis sequences are known to be versatile for the generation of natural product scaffolds and have also been used for ring opening of strained carbo- and heterocycles. In this paper we demonstrate the potential of these reactions for the desymmetrization of 7-azabicycloalkenes. RESULTS We have established efficient protocols for the desymmetrization of different ...

The palladium-catalyzed oxidative desymmetrization of meso dibenzoates yields γ-benzoyloxy cycloalkenones in good yields and with excellent levels of enantioselectivity. These compounds serve as precursors to a broad range of substituted cycloalkenones, including well-established synthetic building blocks and elaborated cycloalkanone derivatives. The ability to prepare both enantiomers of the o...

Enantioselective desymmetrization of meso-aziridines and meso-epoxides with various nucleophiles by organocatalysis has emerged as a cutting-edge approach in recent years. This review summarizes the origin and recent developments of enantioselective desymmetrization of meso-aziridines and meso-epoxides in the presence of organocatalysts.

The desymmetrization of symmetric compounds is a useful approach to obtain chiral building blocks. Readily available precursors with a prochiral unit could be converted into complex molecules with multiple stereogenic centers in a single step. In this review, recent advances in the desymmetrization of symmetric dienes in the diastereotopic group differentiating reaction and its synthetic applic...

We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopen...

We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from a,a-bis(allyl) aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C–H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of avinylcyclopen...

The catalytic addition of alkenes and amines (hydroamination) typically provides α- or β-amino stereocenters directly through C-N or C-H bond formation. Alternatively, desymmetrization reactions of symmetrical aminodialkenes or aminodialkynes provide access to stereogenic centers with the position controlled by the substrate's structure. In the present study of an enantioselective zirconium-cat...

Asymmetric desymmetrization of 4-substituted cyclohexanones using proline amide-catalyzed direct aldol reaction afforded beta-hydroxyketones with three stereogenic centers in high enantioselectivities of up to >99% ee.

A chemical equilibrium model of template-controlled copolymerization is presented for describing the outcome of the experimental induced desymmetrization scenarios recently proposed by Lahav and co-workers.