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マイケル付加およびアルドール反応におけるナノセルロース増強型不斉有機分子触媒反応

ナリハリフェチャ, ジェシカ, ラナイブアリマナナ JESSICA, RANAIVOARIMANANA, NALIHARIFETRA 九州大学

2020.12.31

概要

In the spirit of green chemistry, efforts have been made by chemists toward the elaboration of environmentally friendly processes by creating atom economical reactions or using organocatalysts instead of toxic metal catalysts. Indeed, environmental pollution from chemical industries is raising worldwide concerns. The aim of this dissertation is to use green and sustainable polysaccharide nanofibers to improve the catalytic efficiency and enantioselectivity of various organic reactions in more ecological ways. For this purpose, TEMPO-oxidized cellulose nanofibers (TOCNFs) prepared from wood was chosen, via focusing on the well-defined nanoarchitecture having chiral carbons, high specific surface area and a highly crystalline hydrophobic facet capable of binding various electron-rich compounds. Herein, the (S )-proline catalyzed Michael additions of ketones to nitro olefins and the aldol reactions of ketones with aldehydes were investigated over wood-derived TOCNFs. (S )-Proline is a readily available non-toxic and inexpensive organocatalyst, but poorly catalyzes both reactions, giving a mixture of enantiomers and diastereomers. However, enantio- and diastereo-control is highly desirable as each enantiomer might have different biological activity, and thus both reactions are expected to offer the possibility to synthesize valuable pharmaceutically relevant compounds.

　First, a novel method that substantially enhanced proline-mediated catalysis was successfully developed for the Michael additions of ketones to nitroalkenes through simple incorporation of TOCNFs in the reaction medium at room temperature. The reaction between cyclohexanone and trans-β-nitrostyrene catalyzed by (S)-proline in the presence of TOCNFs yielded 88% of the product with 43% enantioselectivity (ee) versus 35% yield and 32% ee when (S )-proline was used alone. The nanocellulose itself was not catalytically active in the Michael additions. The t rial of different types of matrix with (S)-proline demonstrated the salient role of the highly crystalline structure of TOCNFs with a regular array of carboxylate groups in the increase of the catalytic efficiency. The method was positively applied to different ketones and nitroalkene substrates.

　Furthermore, the catalytic system of TOCNF/(S)-proline performed likewise as a chiral enhancer in direct aldol reactions of 4-nitrobenzaldehyde and cyclopentanone. Despite TOCNF’s being catalytically inactive, the ( R,R)-enantiomer in this reaction was remarkably enriched while the nanofibers were dispersed in the reaction medium, affording 89% ee in the product’s syn form with a very high yield (99%). Nevertheless, nanocellulose-free (S )-proline catalysis resulted in poor selectivity (64% ee, syn form) with a low yield (18%). Two aspects of the enhancement’s mechanism were investigated. The first related to reaction yields showed that TOCNFs prevented proline’s deactivation by inhibiting oxazolidinone formation and other undesirable side polymerization reactions among substrates and/or products. The second part related to enantioselectivity came from molecular dynamics calculations, demonstrating that the aldehyde substrate orientation was governed by carbohydrate–aromatics interactions at the (100) lattice planes of cellulose Iβ surface. The TOCNF/(S )-proline catalyst system favorably enhanced the aldol reactions of different aldehyde substrates.

　To summarize, green organocatalysis occurring on the solid surfaces of nanocellulose bearing regularly aligned chiral carbons on hydrophobic crystalline facets led to highly efficient Michael additions and aldol reactions. Concerted catalysis using polysaccharide nanofibers will bring a fresh perspective into asymmetric synthesis strategies for heterogeneous catalysis . The present study will provide further applications of nanocellulose in sustainable fine chemical productions.

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12. Zhou, P.; Zhang, L.; Luo, S.; Cheng, J.-P. Asymmetric Synthesis of Wieland–Miescher and Hajos–Parrish Ketones Catalyzed by an Amino-Acid-Derived Chiral Primary Amine. J. Org. Chem. 2012, 77, 2526–2530.

13. Zeng, X.P.; Cao, Z.Y.; Wang, Y.H.; Zhou, F.; Zhou, J. Catalytic Enantioselective Desymmetrization Reactions to All-Carbon Quaternary Stereocenters. Chem. Rev. 2016, 116, 7330–7396.

14. List, B.; Hoang, L.; Martin, H.J. Asymmetric Catalysis Special Feature Part II: New mechanistic studies on the proline-catalyzed aldol reaction. Proc. Natl. Acad. Sci. 2004, 101, 5839–5842.

Chapter 6

1. Syu, S.; Kao, T.-T.; Lin, W. A new type of organocatalyst for highly stereoselective Michael addition of ketones to nitroolefins on water. Tetrahedron 2010, 66, 891–897.

2. Kaplaneris, N.; Koutoulogenis, G.; Raftopoulou, M.; Kokotos, C.G. 4-Fluoro and 4- Hydroxy Pyrrolidine-thioxotetrahydropyrimidinones: Organocatalysts for Green Asymmetric Transformations in Brine. J. Org. Chem. 2015, 80, 5464–5473.

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