Catalytic Asymmetric Aerobic Oxidation with Novel Iron Catalyst

• Project/Area Number: 25810065
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: National Institute of Advanced Industrial Science and Technology (2015); Kyushu University (2013-2014)
• Principal Investigator: Matsumoto Kazuhiro 国立研究開発法人産業技術総合研究所, 触媒化学融合研究センター, 研究員 (40512182)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2015: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2014: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2013: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
• Keywords: 合成化学 / 不斉反応 / 酸化反応 / シクロプロパン化 / 鉄 / ルテニウム

Outline of Final Research Achievements

Asymmetric oxidation reactions using novel iron complexes, which have linear ONNO-type trivalent tetradentate ligands constructed from dipyrrin core and two phenol moieties, have been developed. Other asymmetric reactions have been also examined in the presence of transition metal complexes bearing the ONNO-type ligands.
Iron complexes were found to catalyze oxidative kinetic resolution of racemic secondary alcohols. Moreover, ruthenium complexes effectively promoted asymmetric olefin cyclopropanation using diazo compounds as a carbene source, and the desired cyclopropane products were obtained with high enantioselectivity of ca. 90% ee. These results display the efficient asymmetric induction ability of the catalysts with the novel linear ONNO-type trivalent tetradentate ligands.