This review summarizes the tremendous achievemento in the field of catalytic enantioselective Michael additions over the last few years. An impressive number of efficient catalytic systems has been established which are complementary to each other with respect to applicable Michael acceptors and donors. Copper phosphorus amidites, phosphites and phosphonates are the catalysts of choice for the highly enantioselective transfer of (functionalized or unfunctionalized) alkyl groups to cyclic and linear enones. For the corresponding arylations and alkenylations, however, Rhodium-BINAP catalysts are superior. Remarkably, efficient catalytic systems for Michael additions of malonates and other soft nucleophiles include copper(II) bisoxazolines and heterobimetal complexes. Very recently, even metal-free catalysts (e.g., alkaloids and peptides) are gaining importance for enantioselective Michael additions. Several applications of these catalysts in natural product syntheses document the high standard now reached in this field.
The use of gold in homogeneous catalysis is a relatively new field of transition metal catalysis, but has already witnessed spectacular achievements. By virtue of their unique ability to activate carbon–carbon double and triple bonds as soft, carbophilic Lewis acids, gold salts are highly efficient catalysts for the formation of C–C, C–O, C–N, and C–S bonds. Moreover, they are capable of activating C–H bonds of aromatic and other substrates, opening unprecedented pathways for their functionalisation. By using chiral allenes as substrates, gold catalysts can even be applied in stereoselective target-oriented synthesis.