1,2-trans-Diaminocyclohexane (DACH) in Asymmetric Catalysis: Nearing Fifty Years of Faithful Service and Counting

Abstract This review highlights the use of DACH as a versatile ligand in catalytic asymmetric transformations providing mechanistic rationales and relevant comments presented in chronological order for each of the 21 reaction types with references up to December 25, 2023. Intended to be as practically comprehensive as possible, this review assembles useful examples of using DACH as a ligand in organocatalytic or as metal complexes in asymmetric transformations. The resulting enantiomerically enriched, if not pure, chiral non-racemic small molecules are of great utility as value added intermediates in the total synthesis of natural products, in the design and synthesis of medicinally important compounds, and in other areas in organic and bioorganic chemistry where chirality plays a role. The graphic image depicts Spartacus with his arms folded in the same sense of chirality as (R,R)-DACH. 1 Introduction 2 DACH: A Brief Historical Narrative 3 Catalytic Asymmetric Hydrogenation of Alkenes 4 Catalytic Asymmetric Dihydroxylation of Alkenes 5 Catalytic Asymmetric Sulfoxidation and Sulfimidation 6 Catalytic Asymmetric 1,4-Conjugate Addition 6.1 Using Jacobsen’s DACH Metal–salen Complexes as Catalysts 6.2 Using Takemoto’s Bifunctional H-Bonding DACH Thiourea Organocatalyst 6.3 Using DACH Ni(II) Complexes as Catalysts 6.4 Using DACH H-Bonding Catalysis 7 Catalytic Asymmetric Epoxidation of Alkenes 8 Catalytic Asymmetric Claisen Rearrangement 9 Catalytic Asymmetric 1,2-Nucleophilic Addition to Carbonyl Compounds 9.1 Catalytic Asymmetric Addition of Dialkylzinc to Aldehydes and Ketones 9.2 Catalytic Asymmetric Alkynylation of Aldehydes and Ketones 9.3 Catalytic Asymmetric Addition of Cyanide to Aldehydes and Ketones 10 Catalytic Asymmetric Allylic Alkylation 11 Catalytic Asymmetric Cyclopropanation of Alkenes 12 Catalytic Asymmetric Cycloaddition Reactions 13 Catalytic Asymmetric Aziridination of Alkenes 14 Catalytic Asymmetric Hydrogenation of Prochiral Ketones and Imines 15 Catalytic Asymmetric Aldol Reactions 16 Catalytic Asymmetric Opening of Small Ring Systems 16.1 Desymmetrization of meso-Epoxides and meso-Aziridines 16.2 Kinetic Resolution of Racemic Epoxides 16.3 Enantioselective Addition of CO2 to Epoxides 16.4 Enantioselective Ring Opening of Oxetanes 17 Catalytic Asymmetric Strecker Reactions 18 Catalytic Asymmetric Mannich Reactions 19 Catalytic Asymmetric Henry and Aza-Henry Reactions 20 Catalytic Asymmetric Morita–Baylis–Hillman and Rauhut–Currier Reactions 21 Catalytic Asymmetric Petasis Reactions 22 Organocatalytic Asymmetric Cascade Reactions 23 Miscellaneous Catalytic Reactions 24 Conclusion and Outlook 25 DACH Catalysts and Ligands List

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