报告题目：CO₂Incorporation Reactions and CO₂Mediated Reactions

报告人：Prof. Tohru Yamada, Department of Chemistry, Keio University，Japan

报告时间：2019年11月10日（周日）上午10:00 - 11:00

报告地点：19号楼226学术报告厅

报告人简介：

        1987 Ph.D., The University of Tokyo (Prof. Teruaki Mukaiyama)

1987-1997 Researcher for Basic Research Lab of Mitsui Petrochemical Ind. Ltd.

1997-2002 Associate Professor at Department of Chemistry, Keio University

2002-current Professor at Department of Chemistry, Keio University

Prof.Tohru Yamada’s research includenew synthetic reactions catalyzed by metal complexes, e.g. catalytic enantioselective reduction, carbon dioxide fixation for organic synthesis, and microwave application to organic synthesis.

报告内容：

A silver/base catalyst system was developed to effectively activate alkyne derivatives to capture CO2. We reported that the combined use of a catalytic amount of silver acetate and DBU efficiently catalyzed the incorporation of CO2 under mild reaction conditions for a wide range of propargyl alcohols to afford the corresponding cyclic carbonates in high-to-excellent yields. This procedure can be applied to various alkyne containing substrates to afford the corresponding heterocycles. In this reaction, the corresponding α,β-unsaturated carbonyl compounds generated via a decarboxylative Meyer-Schuster type reaction were realized in some polar solvents, such as form amides.

Recently, we reported the decarboxylative Nazarov type reaction to afford the highly substituted 2-cyclopentenones from the corresponding cyclic carbonate, prepared with the silver-catalyzed CO2 incorporation into propargyl alcohol derivatives. When the carbonate was treated with a catalytic amount of BF3•OEt2 in 1,2-dichloroethane at room temperature, the Nazarov cyclization proceeded to afford trans-2-cyclopentenones with high stereoselectivity and in high yield.8 This procedure can be applied to the chirality transfer system to afford the corresponding 2-cyclopentenones in optically pure form.

References

(1) W. Yamada, Y. Sugawara, H.-M. Chen, T. Ikeno, T. Yamada,Eur. J. Org. Chem.2007,

2604-2607; Y. Sugawara, W. Yamada, S. Yoshida, T. Ikeno, T. Yamada,J. Am. Chem. Soc.2007,129, 12902-12903; S. Yoshida, K. Fukui, S. Kikuchi, T. Yamada,J. Am. Chem. Soc.2010,132, 4072-4073.

(2) a) S. Kikuchi, K. Sekine, T. Ishida, T. Yamada,Angew. Chem. Int. Ed.2012, 51,6989-6992; b) K. Sekine, A. Takayanagi, S. Kikuchi, T. Yamada,Chem. Commun.2013,49, 11320-11322.

(3) T. Ishida, S. Kikuchi, T. Tsubo, T. Yamada,Org. Lett.2013,15, 848-851.

(4) T. Ishida, S. Kikuchi, T. Yamada,Org. Lett.2013,15, 3710-3713.

(5) T. Ishida, R. Kobayashi, T. Yamada,Org. Lett.2014,16, 2430-2433.

(6) K. Sekine, Y. Sadamitsu, T. Yamada,Org. Lett.2015,17, 5706-5709.

(7) Y. Sadamitsu, K. Komatsuki, K. Saito, T. Yamada,Org. Lett.2017,19, 3191-3194.

(8) K. Komatsuki, Y. Sadamitsu, K. Sekine, K. Saito, T. Yamada,Angew. Chem. Int. Ed.2017,56, 11594-11598.