The Yamashita Group@NU
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Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
Department of Molecular and Macromolecular Chemistry,
Graduate School of Engineering, Nagoya University
access to Higashiyama campus, campus map
#1 Building, room 1029 (10th floor, entrance is the 2nd floor)

(2d) Development of new homogeneous catalyst reforming the present petrochem processes

(2d-1) Synthesis of formic acid by hydrogenation of carbon dioxide
Formic acid is an important chemical product used as a preservative and an insecticide as well as for tanning leathers. In addition, formic acid plays a major role in synthetic chemistry as an acid, a reductant, and a carbon source. In industrial processes, formic acid is mainly synthesized by carbonylation of alcohols using carbon monoxide followed by hydrolysis, which requires a high pressure of toxic carbon monoxide gas. We recently achieved an effective hydrogenation of carbon dioxide using a newly-prepared iridium catalyst using PNP-pincer complexes. The highest turnover number (TON) reached as high as 3,500,000, which is the best activity among reported catalysts.

1) Tanaka, R.; Yamashita, M.; Nozaki, K. J. Am. Chem. Soc. 2009, 131, 14168-14169. doi
2) Tanaka, R.; Yamashita, M.; Chung, L. W. ; Morokuma, K.; Nozaki, K. Organometallics, 2011, 30, 6742-6750.   doi

(2d-2) Sequential hydroformylation of alkan/hydrogenation of aldehyde to foraliphatic linear alcohols
Linear 1-alkanols (n-alcohols) are widely used in industry as precursors of detergents and plasticizers. Current industrial production of n-alcohols mostly employs a two-step process consisting of hydroformylation of terminal olefins, purification of n-aldehydes, and then hydrogenation of n-aldehydes to n-alcohols. A one-pot process would be advantageous over the two-step process. We recently found an effective catalyst system consisting two orthogonal catalysts to achive this tandem transformation. Mixing Rh and Ru catalyst led to a formation of n-alcohols by a reaction of 1-alkene with syn-gas.

1) Takahashi, K.; Yamashita, M.; Ichihara, T.; Nakano, K.; Nozaki, K. Angew. Chem. Int. Ed., 2010,49, 4488-4490. doi.
2) Takahashi, K.; Yamashita, M.; Tanaka, Y.; Nozaki, K. Angew. Chem. Int. Ed. 2012, 51, 4383-4387.   doi
3) Takahashi, K.; Yamashita, M.; Nozaki, K. J. Am. Chem. Soc. 2012, 134, 18746-18757.   doi