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

A highly regio- and enantioselective allylic C–H alkylation of 1,4-dienes with glycine Schiff bases has been established by chiral palladium-phosphoramidite catalysis. This reaction can proceed under mild conditions and tolerate a wide scope of 1,4-dienes, delivering structurally diverse chiral β-branched α-amino acid surrogates in moderate to high yields and with high levels of regio-, Z / E -, diastereo- and enantioselectivities.

Palladium-catalyzed asymmetric allylic C-H alkylation of 1,4-dienes and glycine Schiff bases

N‐Heterocyclic Carbene/Copper Cooperatively Catalyzed Asymmetric Synthesis of Spirooxindoles

Catalytic kinetic resolution (KR) and dynamic kinetic asymmetric transformation (DyKAT) are alternative and complementary avenues to access chiral stereoisomers of both starting materials and reaction products. The development of highly efficient chiral catalytic systems for kinetically controlled processes has therefore been one of the linchpins in asymmetric synthesis. N-heterocyclic carbene (NHC)/copper cooperative catalysis has enabled highly efficient KR and DyKAT of racemic N-tosylaziridines by [3+3] annulation with isatin-derived enals, leading to highly enantioenriched N-tosylaziridine derivatives (up to >99 % ee) and a large library of spirooxindole derivatives with high structural diversity and stereoselectivity (up to >95:5 d.r., >99 % ee). Mechanistic studies suggest that the NHC can bind reversibly to the copper catalyst without compromising its catalytic activity and regulate the catalytic activity of the copper complex to switch the chemoselection between KR and DyKAT.

Liu-Zhu Gong

Papers

Palladium-catalyzed asymmetric allylic C-H alkylation of 1,4-dienes and glycine Schiff bases

N‐Heterocyclic Carbene/Copper Cooperatively Catalyzed Asymmetric Synthesis of Spirooxindoles

Kinetic Resolution of Aziridines Enabled by N‐Heterocyclic Carbene/Copper Cooperative Catalysis: Carbene Dose‐Controlled Chemo‐Switchability

Enantioselective Functionalization of Inactive sp(3) C-H Bonds Remote to Functional Group by Metal/Organo Cooperative Catalysis.

Palladium-catalyzed enantioselective carboannulation of 1,3-dienes with aryl iodides enables access to chiral indanes.