Alkenes asymmetric dicarbonylation

The popularity of Cu(acac)2, where acac = acetylacetonato, as a precatalyst in alkene cyclopropanation using diazoesters has led to the investigation of chiral 1,3-dicarbonyls as a source of asymmetric induction in this process. Mathn et al. (26) report a selective cyclopropanation of styrene with a dimedone-derived diazocarbonyl in the presence of a camphor-derived diketone, Eq. 12. The reaction is con-... 

Dicarbonylation can also provide access to lactones in which a 1,2-diester is formed directly from a C=C or C=C bond. In both cases, an oxidant is required for the regeneration of Pd(II) from Pd(0) (Scheme 2.17) [38-40]. Ukaji et al. demonstrated the first asymmetric intramolecular alkene dicarbonylation using a chiral bisoxazo-line ligand with Cu(I) and O2 as the oxidant (Scheme 2.18) [41]. 

Conjugate addition of carbon nucleophiles to electron-poor alkenes is of paramount importance among the enormous community of synthetic processes devoted to carbon-carbon bond formation. In particular, asymmetric Michael additions between a,(S-unsaturated ketone (enone) and 1,3-dicarbonyl compounds allow for access to a variety of optically active adducts affording synthetically useful motifs for the preparation of biologically active natural products and pharmaceutically attractive intermediates (Scheme 9.1). 

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