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

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

Copper salts have been developed as versatile catalysts for oxidative coupling reactions in organic synthesis. During these processes, Cu-catalysts are often proposed to serve as a one-electron oxidant to promote the single-electron transfer process. Recently, the transition-metal catalyzed direct dehydrogenative transformation has attracted considerable attention. This tutorial review summarizes the recent advances in the copper-catalyzed dehydrogenative functionalization via a single electron transfer (SET) process achieving C–C, C–N, C–O, C–halogen atoms, C–P, and N–N bond formation.

Recent advances in copper-catalyzed dehydrogenative functionalization via a single electron transfer (SET) process.

The title reaction of 3,3′-bisindolin-2-ones with vinylcarbamates catalyzed by a chiral phosphoric acid affords the corresponding indolinones with concomitant generation of an all-carbon quaternary stereogenic center in high yield and excellent enantioselectivity.

Core-structure-oriented asymmetric organocatalytic substitution of 3-hydroxyoxindoles: application in the enantioselective total synthesis of (+)-folicanthine.

Enantioselective Oxidative Cross-Coupling Reaction of 3-Indolylmethyl CH Bonds with 1,3-Dicarbonyls Using a Chiral Lewis Acid-Bonded Nucleophile to Control Stereochemistry

Organocatalytic enantioselective Biginelli and Biginelli-like reactions by chiral phosphoric acids derived from 3,3′-disubstituted binaphthols have been investigated. The size of 3,3′-substituents of the catalysts is able to control the stereochemistry of the Biginelli reaction. By tuning the 3,3′-disubstituents of the phosphoric acids, the stereochemistry of the Biginelli reaction can be reversed. This organocatalytic Biginelli reaction by Bronsted acids 12b and 13 is applicable to a wide range of aldehydes and various β-keto esters, providing a highly enantioselective method to access DHPMs. 3,3′-Di(triphenylsilyl) binaphthol-derived phosphoric acid afforded Biginelli-like reactions of a broad scope of aldehydes and enolizable ketones with benzylthiourea, giving structurally diverse dihydropyrimidinethiones with excellent optical purity. Theoretical calculations with the ONIOM method on the transition states of the stereogenic center forming step showed that the imine and enol were simultaneously activa...

https://pubs.acs.org/doi/pdf/10.1021/ja105157b

Highly Enantioselective Organocatalytic Biginelli and Biginelli-Like Condensations: Reversal of the Stereochemistry by Tuning the 3,3′-Disubstituents of Phosphoric Acids

An asymmetric catalytic decarboxylative [4+2] annulation of 4-ethynyl dihydrobenzooxazinones and carboxylic acids has been established by cooperative copper and nucleophilic Lewis base catalysis. A C1 ammonium enolate and copper–allenylidene complex, each catalytically generated from different substrates, underwent a cascade asymmetric propargylation and lactamization process to yield optically active 3,4-dihydroquinolin-2-one derivatives with excellent levels of stereoselectivity (up to 99 % ee, 95:5 d.r.).

Asymmetric [4+2] Annulation of C1 Ammonium Enolates with Copper-Allenylidenes.

Highly enantioselective [3+3] and [3+4] annulations of isatin-derived enals with ethynylethylene carbonates and ethynyl benzoxazinanones are enabled by NHC/cooper cooperative catalysis, leading to a big library of spirooxindole derivatives in high structural diversity and enantioselectivity (up to 99 % ee). Both reactions represent a nicely synergistic integration of NHC and copper catalysis, in which both catalysts activate the substrates and the chiral NHC perfectly controls the stereochemistry.

Jin Song

Papers

Core-structure-oriented asymmetric organocatalytic substitution of 3-hydroxyoxindoles: application in the enantioselective total synthesis of (+)-folicanthine.

Enantioselective Oxidative Cross-Coupling Reaction of 3-Indolylmethyl CH Bonds with 1,3-Dicarbonyls Using a Chiral Lewis Acid-Bonded Nucleophile to Control Stereochemistry

Highly Enantioselective Organocatalytic Biginelli and Biginelli-Like Condensations: Reversal of the Stereochemistry by Tuning the 3,3′-Disubstituents of Phosphoric Acids

Asymmetric [4+2] Annulation of C1 Ammonium Enolates with Copper-Allenylidenes.

N-Heterocyclic Carbene/Copper Cooperative Catalysis for the Asymmetric Synthesis of Spirooxindoles