Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds

Asymmetric enamine catalysis.

3.1. C-M and X-H as Nucleophiles 1806 3.2. C-H and X-M as Nucleophiles 1809 3.2.1. C-Halogen Bond Formations 1809 3.2.2. C-O Bond Formations 1812 3.3. C-H and X-H as Nucleophiles 1812 3.3.1. C-O Bond Formations 1812 3.3.2. C-N Bond Formations 1815 4. Oxidative X-X Bond Formations between Two Nucleophiles 1819 5. Conclusions 1819 Author Information 1819 Biographies 1819 Acknowledgment 1820 References 1820

Bond Formations between Two Nucleophiles: Transition Metal Catalyzed Oxidative Cross-Coupling Reactions

Over the last decade, substantial research has led to the introduction of an impressive number of efficient procedures which allow the selective construction of CC bonds by directly connecting two different CH bonds under oxidative conditions. Common to these methodologies is the generation of the reactive intermediates in situ by activation of both CH bonds. This strategy was introduced by the group of Li as cross-dehydrogenative coupling (CDC) and discloses waste-minimized synthetic alternatives to classic coupling procedures which rely on the use of prefunctionalized starting materials. This Review highlights the recent progress in the field of cross-dehydrogenative C sp 3C formations and provides a comprehensive overview on existing procedures and employed methodologies.

The Cross-Dehydrogenative Coupling of C sp 3H Bonds: A Versatile Strategy for CC Bond Formations

Complete Field Guide to Asymmetric BINOL-Phosphate Derived Brønsted Acid and Metal Catalysis: History and Classification by Mode of Activation; Brønsted Acidity, Hydrogen Bonding, Ion Pairing, and Metal Phosphates

/pdf/asymmetric-nitroallylation-of-arylboronic-acids-with-4imubg2a0y.pdf

Asymmetric Nitroallylation of Arylboronic Acids with Nitroallyl Acetates Catalyzed by Chiral Rhodium Complexes and Its Application in a Concise Total Synthesis of Optically Pure (+)‐γ‐Lycorane.

The Proline‐Catalyzed Mannich Reaction and the Advent of Enamine Catalysis

A tandem dehydrative cyclization/aza-hetero-Diels–Alder reaction catalyzed by gold(I) complex bearing BINOL-derived chiral phosphoramidite ligand has been developed. With this method, optically active chiral bicyclic tetrahydropyridazine derivatives could be obtained in one step from readily available starting materials.

Chiral Gold Complex Catalyzed Tandem Dehydrative Cyclization/Hetero-Diels–Alder Reaction

In addition to the title reaction, a unique sp3 C—H-activation-based approach is presented which provides access to an oxindole derivative bearing a quaternary stereogenic center with high optical purity.

Enantioselective Oxidative Cross‐Coupling Reaction of 3‐Indolylmethyl C—H Bonds with 1,3‐Dicarbonyls Using a Chiral Lewis Acid‐Bonded Nucleophile to Control Stereochemistry.

Chiral indoline-2-carboxylic acid has been identified to enable a highly enantioselective Catellani-type annulation of (hetero)aryl, alkenyl triflate and conjugated vinyl iodides with 4-(bromomethyl)cyclohexanone, directly assembling a diverse range of chiral all-carbon bridged ring systems. Control experiments and DFT calculations suggest that the coordinating orientation of the chiral amino acid to the arylpalladium(II) center allows for high levels of stereochemical control.

Liu-Zhu Gong

Papers

Asymmetric Nitroallylation of Arylboronic Acids with Nitroallyl Acetates Catalyzed by Chiral Rhodium Complexes and Its Application in a Concise Total Synthesis of Optically Pure (+)‐γ‐Lycorane.

The Proline‐Catalyzed Mannich Reaction and the Advent of Enamine Catalysis

Chiral Gold Complex Catalyzed Tandem Dehydrative Cyclization/Hetero-Diels–Alder Reaction

Enantioselective Oxidative Cross‐Coupling Reaction of 3‐Indolylmethyl C—H Bonds with 1,3‐Dicarbonyls Using a Chiral Lewis Acid‐Bonded Nucleophile to Control Stereochemistry.

Chiral Indoline-2-carboxylic Acid Enables Highly Enantioselective Catellani-type Annulation with 4-(bromomethyl)cyclohexanone