4.3. Reaction Mechanism 2373 4.4. Asymmetric Synthesis 2374 4.5. Outlook 2374 5. Alternating Polymerization of Oxiranes and CO2 2374 5.1. Reaction Outlines 2374 5.2. Catalyst 2376 5.3. Asymmetric Polymerization 2377 5.4. Immobilized Catalysts 2377 6. Synthesis of Urea and Urethane Derivatives 2378 7. Synthesis of Carboxylic Acid 2379 8. Synthesis of Esters and Lactones 2380 9. Synthesis of Isocyanates 2382 10. Hydrogenation and Hydroformylation, and Alcohol Homologation 2382

Transformation of carbon dioxide.

C-C, C-O, C-N bond formation on sp2 carbon by Pd(II)-catalyzed reactions involving oxidant agents.

Pd -catalyzed oxidative coupling with organometallic reagents via C–H activation

Carbon dioxide is an important carbon source in the atmosphere and is “problematic” toward the activities of human beings. Although carbon dioxide is a cheap, abundant and relatively nontoxic C1 source, its chemical transformations have not been widely developed so far and are still far from synthetic applications, especially in the construction of the C–C bond. This critical review summarizes the recent advances on transition-metal-catalyzed C–C bond formation through the fixation of carbon dioxide and their synthetic applications (124 references).

Transition-metal-catalyzed C–C bond formation through the fixation of carbon dioxide

Synthesis of secondary amines

Efficient carbamate synthesis via a three-component coupling of an amine, CO2, and alkyl halides in the presence of Cs2CO3 and tetrabutylammonium iodide.

We report herein a mild and efficient method for carbon-carbon bond formation between aryl stannanes and olefins via Pd(II) catalysis in the presence of oxygen or Cu(II) oxidants as a reoxidant. The process allows reactions between various olefins and aryl stannanes of varying electron density. Coupling methods under these oxidation conditions are comparatively described, and the benefits and limitations are also discussed.

Seung Il Shin

Papers

Efficient carbamate synthesis via a three-component coupling of an amine, CO2, and alkyl halides in the presence of Cs2CO3 and tetrabutylammonium iodide.

Mild and efficient aryl-alkenyl coupling via Pd(II) catalysis in the presence of oxygen or Cu(II) oxidants.

CsOH-promoted chemoselective mono-N-alkylation of diamines and polyamines

Efficient and selective N-alkylation of carbamates in the presence of Cs2CO3 and TBAI

Energy Transfer Photocatalytic Radical Rearrangement in N-Indolyl Carbonates.