Laboratory for Computational and Experimental CatalysisDepartment of Chemistry College of Science Rikkyo University


The increasing importance of enantiopure molecules in pharmaceutical and medicinal chemistry has stimulated the development of new and efficient asymmetric calalyst. An exhaustive screening of catalysts is generally required to identify the best asymmetric catalyst. Theoretical calculation enables the visualization of appropriate catalysts to elucidate their electronic and structural properies. Recent development of computational methods, software, and hardware enables accurate calculations and allows not only explanation but also prediction of stereoselectivity even in large molecular system. Therefore, theoretical calculation play an increasingly important role in the design of asymetric catalyst. In our laboratory, well-designed asymmetric catalysts are developed with aid of theoretical calculations.

Development of Asymmetric Catalyst

"Chiral Zn(II)-Bisamidine Complex as a Lewis-Bronsted Combined Acid Catalyst:
Application to Asymmetric Mukaiyama Aldol Reactions of a-Ketoesters"

Gotoh, R.; Yamanaka, M.
Molecules 2012, 17, 9010-9022.

Computational Study of Stereocontrol Mechanism

"PyBidine-Cu(OTf)2-Catalyzed Asymmetric [3+2] Cycloaddition with Imino Esters: Harmony of Cu-Lewis Acid and Imidazolidine-NH Hydrogen Bonding in Concerto Catalysis"

Arai, T.; Ogawa, H.; Awata, A.; Sato, M.; Watabe, M.; Yamanaka, M.
Angew. Chem. Int. Ed. 2015, 54, 1595-1599.

"Origin of High E-Selectivity in 4-Pyrrolidinopyridine-Catalyzed Tetrasubstituted a,a'- Alkenediol: A Computational and Experimental Study"

Yamanaka, M.; Yoshida, U.; Sato, M.; Shigeta, T.; Yoshida, K.; Furuta, T.; Kawabata, T.
J. Org. Chem. 2015, 80, 3075-3082.

"Origin of Stereocontrol in Guanidine-Bisurea Bifunctional Organocatalyst That Promotes a- Hydroxylation of Tetralone-Derived b-Ketoesters: Asymmetric Synthesis of b- and g-Substituted Tetralone Derivatives via Organocatalytic Oxidative Kinetic Resolution"

Odagi,M.; Furukori, K.; Yamamoto, Y.; Sato, M.; Iida, K.; Yamanaka, M.; Nagasawa, K.
J. Am.Chem. Soc. 2015, 137, 1909-1915.

"DFT Studies ofMechanism and Origin of Stereoselectivity of Palladium-Catalyzed CyclotrimerizationReactions Affordingsyn-Tris(norborneno)benzenes"

Yamanaka, M.; Morishima, M.; Shibata, Y.; Higashibayashi, S.; Sakurai, H.
Organometallics2014, 33,3060-3068.

"Mechanistic study ofasymmetric Michael addition of malonates to enones catalyzed by a primary aminoacid lithium salt"

Yoshida, M.; Nagasawa, Y.; Kubara, A.; Hara, S.; Yamanaka, M.
Tetrahedron2013, 69, 10003-10008.

"Investigation of the Carboxylate Position during the Acylation Reaction Catalyzed by Biaryl DMAP Derivatives with an InternalCarboxylate"

Nishino, R.; Furuta, T.; Kan K.; Sato, M.; Yamanaka, M.; Sasamori, T.; Tokitoh, N.; Kawabata, T.
Angew. Chem. Int. Ed. 2013, 52, 6445-6449.

"DFT Study of Mechanism and Origin of Enantioselectivity in Chiral BINOL-Phosphoric Acid Catalyzed Transfer Hydrogenation of Ketimine and a-Imino Ester Using Benzothiazoline"

Shibata, Y.; Yamanaka, M.
J. Org. Chem. 2013, 78, 3731-3736.

"Enantioselective Synthesis of Multisubstituted Biaryl Skeleton by Chiral Phosphoric Acid Catalyzed Desymmetrization/KineticResolution Sequence"

Mori, K.; Ichikawa, Y.; Kobayashi, M.; Shibata, Y.; Yamanaka, M.; Akiyama, T.
J. Am. Chem. Soc. 2013,135, 3964-3970.

"Kinetic Resolution in Chiral Bronsted Acid Catalyzed AldolReaction: Enantioselective Robinson-type Annulation Reaction"

Akiyama, T.; Yamanaka, M.; Hoshino, M.; Katoh, T.; Mori, K.
Eur. J. Org. Chem. 2012, 24, 4508-4514.

"DFT Study of Chiral Phosphoric Acid Catalyzed Enantioselective Friedel-Crafts Reaction of Indole with Nitroalkene:Bifunctionality and Substituent Effect of Phosphoric Acid"

Hirata, T.; Yamanaka, M.
Chem. Asian. J. 2011, 6, 510-516.

"DFT Study on Bifunctional Chiral Bronsted Acid-CatalyzedAsymmetric Hydrophosphonylation of Imines"

Yamanaka, M.; Hirata, T.
J. Org. Chem. 2009, 74, 3266-3271.

"Chiral Bronsted Acid-catalyzed Enantioselective Mannich-typeReaction"

Yamanaka, M.; Itoh, J.; Fuchibe, K.; Akiyama, T.
J. Am. Chem. Soc. 2007, 129, 6756-6764.