Laboratory for Computational and Experimental Catalysis
Department of Chemistry College of Science Rikkyo University特徴的な共鳴安定化構造と多様な配位様式を有するビスアミジン骨格に着目して、複合的な機能を有する新しい不斉分子触媒を開発しています。このビスアミジン骨格を鋳型とする不斉分子触媒は、異なる酸触媒部位（ブレンステッド酸とルイス酸）や複数の金属触媒部位を有しており、それぞれの触媒部位が協力することで、単一の触媒部位のみで構成される分子触媒を超える反応性や立体選択性を達成します。触媒の活性度を数字で表せば、それぞれ"１"の触媒部位が足し合わさった複合機能型不斉分子触媒は、単純な"１＋１＝２"ではなく、互いに協力して反応基質を活性化したり、役割分担をして反応を促進させることで、"３"にも"４"にもなることが期待できます。特にその応用として、合成化学的に有用であるにもかかわらず未開拓な領域であるα－ケトエステルに対する触媒的不斉合成反応に取り組んでいます。
"Chiral Bipyridine Ligand with Flexible Molecular Recognition Site: Development and Application to Copper-Catalyzed Asymmetric Borylation of α,β-Unsaturated Ketones"
Tsutsumi, R.; Taguchi, R.; Yamanaka, M.
ChemCatChem, 2022, 14, e202101278
"Multinuclear Zinc Bisamidinate Catalyzed Asymmetric Alkylation of α-Ketoesters and Its Unique Chemoselectivity"
Yamanaka, M.; Inaba, M.; Gotoh, R.; Ueki, Y.; Matsui, K.
Chem. Commun. 2017, 53, 7513-7516.
"Chiral Zn(II)-Bisamidine Complex as a Lewis-Bronsted Combined Acid Catalyst:
Application to Asymmetric Mukaiyama Aldol Reactions of α-Ketoesters"
Gotoh, R.; Yamanaka, M.
Molecules 2012, 17, 9010-9022.
望みの光学異性体のみを選択的に合成する不斉分子触媒を合理的に開発していくためには、"立体選択性の原因は何か？"という疑問を明らかにすることが重要です。近年では、反応の本質を捉えたモデル系から実験結果の解析に不可欠な置換基や溶媒を考慮した大規模な実在系まで、より精密に量子化学計算を行うことが可能です。触媒的不斉合成反応を中心に、量子化学計算により反応機構の詳細から立体選択性の原因を解明しています。
"Catalyst-Dependent Rate-Determining Steps in Regiodivergent Vinylogous Aza-Morita-Baylis-Hillman Reactions with N-Ts Imines"
Gondo, N.; Hyakutake, R.; Fujimura, K.; Ueda, Y.; Nakano, K.; Tsutsumi, R.; Yamanaka, M.; Kawabata, T.
Asian J. Org. Chem. 2022, 11, e2021005.
"Mechanistic insights into entropy-driven 1,2-type Friedel-Crafts reaction with conformationally flexible guanidine-bisthiourea bifunctional organocatalysts"
Nakano, K.; Orihara, T.; Kawaguchi, M.; Hosoya, K.; Hirao, S.; Tsutsumi, R.; Yamanaka, M.; Odagi, M.; Nagasawa, K.
Tetrahedron 2021, 92, 132281.
"Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric Halolactonization"
Arai, T.; Horigane, K.; Watanabe, O.; Kakino, J.; Sugiyama, N.; Makino, H.; Kamei, Y.; Yabe, S.; Yamanaka, M.
iScience 2019, 12, 280-292.
"Origin of High Regio-, Diastereo-, and Enantioselectivities in 1,6-Addition of Azlactones to Dienyl N-Acylpyrroles: A Computational Study"
Yamanaka, M.; Sakata, K.; Yoshioka, K.; Uraguchi, D.; Ooi, T.
J. Org. Chem. 2017, 82, 541-548.
"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.
