Laboratory for Organic Reaction Chemistry

Tetsuya Satoh (Professor)

1. Current Research and Principal Research Interests

1-1. Development of Environmentally-Benign Cross-Coupling Reactions
Transition-metal-catalyzed cross-coupling reactions have been recognized as highly useful tools for the syntheses of pi-conjugated molecules. However, the conventional cross-coupling method has the following weak points: 1) the formation of stoichiometric amounts of salt-wastes is usually involved and 2) starting materials such as aromatic halides and arylmetal reagents are not always readily available. This work targets the development of environmentally-benign, waste-free dehydrogenative cross-coupling reactions of widely available aromatic hydrocarbons with unsaturated compounds under air. New catalyst systems consisting of rhodium or ruthenium complexes for the dehydrogenative cross-coupling have already been developed.

Recently, oxygen, nitrogen, and other heteroatom-containing substituents (–LH) have been found to act as directing groups to induce chelation-assisted C–H bond cleavage. They allow smooth coupling at the neighboring position. Especially in the coupling with alkynes, a variety of fused heterocyclic compounds can be constructed in a single step.

1-2. Organic Synthesis Using Readily Available Building Blocks
Fossil resources including petroleum, coal, and natural gas are currently predominant raw materials for the production of chemicals in modern society. However, in the near future, we have to develop the chemicals feeding system based on renewable resources such as biomass. The change of feedstock requires new organic synthetic methods. We now focus on carboxylic acids as readily available building blocks from biomass. A number of new reactions enabling the efficient transformation of carboxylic acids to various functionalized molecules have been developed by our group.

2. Selected Publications

1. "Rhodium-Catalyzed Dehydrogenative Coupling of Phenylheteroarenes with Alkynes or Alkenes", Iitsuka, T.; Hirano, K.; Satoh, T.; Miura, M., J. Org. Chem., 80, pp. 2804-2814 (2015).

2. "Synthesis of Fluorene Derivatives through Rhodium-Catalyzed Dehydrogenative Cyclization", Morimoto, K.; Itoh, M.; Hirano, K.; Satoh, T.; Shibata, Y.; Tanaka, K.; Miura, M., Angew. Chem. Int. Ed., 51, pp. 5359-5362 (2012).

3. "Oxidative Coupling of Aromatic Substrates with Alkynes and Alkenes under Rhodium Catalysis", Satoh, T.; Miura, M., Chem. Eur. J., 16, pp. 11212-11222 (2010).

4. "Fluorescent naphthyl- and anthrylazoles from the catalytic coupling of phenylazoles with internal alkynes through the cleavage of multiple C-H bonds", Umeda, N.; Tsurugi, H.; Satoh, T.; Miura, M., Angew. Chem. Int. Ed., 47, pp. 4019-4022 (2008).

5. "An efficient waste-free oxidative coupling via regioselective C-H bond cleavage: Rh/Cu-catalyzed reaction of benzoic acids with alkynes and acrylates under air", Ueura, K.; Satoh, T.; Miura, M., Org. Lett., 9, pp. 1407-1409 (2007).

6. "Catalytic Direct Arylation of Heteroaromatic Compounds", Satoh, T.; Miura, M., Chem. Lett., 36, pp. 200-205 (2007).

7. "Palladium-catalyzed multiple arylation of thiophenes", Okazawa, T.; Satoh, T.; Miura, M.; Nomura, M., J. Am. Chem. Soc., 124, pp. 5286-5287 (2002).

8. "Iridium-catalyzed reaction of aroyl chlorides with internal alkynes to produce substituted naphthalenes and anthracenes", Yasukawa, T.; Satoh, T.; Miura, M.; Nomura, M., J. Am. Chem. Soc.. 124, pp. 12680-12681 (2002).

9. "Palladium-catalyzed arylative carbon-carbon bond cleavage of alpha,alpha-disubstituted arylmethanols", Terao, Y.; Wakui, H.; Satoh, T.; Miura, M.; Nomura, M., J. Am. Chem. Soc., 123, pp. 10407-10408 (2001).

10. "Palladium-catalyzed regioselective mono- and diarylation reactions of 2-phenylphenols and naphthols with aryl halides", Satoh, T.; Kawamura, Y.; Miura, M.; Nomura, M., Angew. Chem. Int. Ed., 36, pp. 1740-1742 (1997).