Catalytic enantioselective construction of all-carbon quaternary stereocenters

Catalytic enantioselective construction of all-carbon quaternary stereocenters, i.e. carbon atoms bearing four different carbon substituents, poses a particular challenge in organic synthesis. This review gives a comprehensive account on the currently available methods of the above transformation that afford high enantioselectivities and synthetically useful yields. 1 Introduction 2 Cycloadditions 2.1 Diels-Alder Reactions 2.2 [3+2] Cycloadditions 2.3 [2+2] Synthesis of beta-Lactams 2.4 Cyclopropanations 3 Combination of Carbon Nucleophiles and Carbon Electrophiles 3.1 Michael Additions and Direct Alkylations 3.2 Allylation via Palladium pi-Allyl Intermediates 3.3 Copper-Catalyzed S(N)2' Allylations 3.4 Reactions with Carbonyl and Imine Electrophiles 4 Arylation and Vinylation Reactions 4.1 Intramolecular Heck Reactions 4.2 alpha-Arylation and Vinylation Reactions of Ketones and Lactones 4.3 Desymmetrizing Suzuki Couplings 5 Metal-Catalyzed Diene and Enyne Cyclizations 5.1 Diene Cyclizations 5.2 Enyne Cyclizations 6 Intramolecular Hydroacylations 6.1 Intramolecular Stetter Reactions 6.2 Rhodium-Catalyzed Desymmetrization 7 Allylations Mediated by Tertiary Radicals or Cations 8 Rhodium-Catalyzed C-H Insertions 9 Other Desymmetrization Methods 10 Summary and Outlook