Multi-step enzyme-organocatalyst C–C bond forming reactions in deep-eutectic-solvents: towards improved performances by organocatalyst design

Sustainable Chemical Processes

Christoph R Müller¹  Andreas Rosen¹  Pablo Domínguez de María² 

[1] Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringerweg 1, Aachen, 52074, Germany

[2] Sustainable Momentum, SL, Ap. Correos 3517, Las Palmas De Gran Canaria, 35004, Canary Islands, Spain

关键词: Multi-step cascade reaction;    Recycling;    Deep-eutectic-solvents;    Lipases;    Biocatalysis;   

Others  :  1222580
DOI  :  10.1186/s40508-015-0039-0

 received in 2015-04-07, accepted in 2015-07-29,  发布年份 2015

【 摘 要 】

Background

Deep eutectic solvents (DES) have recently emerged as promising non-hazardous environmentally-friendly solvents. In this respect, the use of DES as media for multi-step enzyme-organocatalysis (C–C bond formation via aldol-type reactions) represents a promising sustainable option. Being soluble in DES, organocatalysts may be retained in the DES phase during biphasic extractive work-up (e.g. with biogenic 2-methyl-tetrahydrofuran), enabling product recovery and organocatalyst recycling within the DES phase simultaneously.

Main results

Herein, the proof-of-concept of designing organocatalysts—sspecifically tailored for DES—that may be properly retained in the DES phase (immobilized) among extractive cycles is demonstrated for the first time. To this end, the incorporation of novel hydrogen-bond donor groups (e.g. −OH) in the organocatalyst structure appears as a promising option to achieve improved results, leading to 1.5-fold higher conversions and yields, together with excellent chemoselectivities (>90%) for the new organocatalyst. Reactions are conducted using different bio-based DES, showing the broad applicability and possibilities that these processes may have.

Conclusions and implications

In this work it is demonstrated that organocatalysts can be tuned to be used in different DES. This first proof-of-concept may trigger new research and applications of DES as sustainable solvents for enantioselective C–C bond forming reactions, whereby the organocatalyst design can play an important role for optimized integrated process set-up.

【 授权许可】

   
2015 Müller et al.

【 图 表 】

Fig.1.

Fig.2.

Fig.3.

Fig.4.

Figure 4.

【 参考文献 】

• [1]Gu Y, Jerome F: Bio-based solvents: an emerging generation of fluids for the design of eco-efficient processes in catalysis and organic chemistry. Chem Soc Rev 2013, 42:9550-9570.
• [2]Zhang Q, De Oliveira Vigier K, Boyer S, Jerome F: Deep eutectic solvents: syntheses, properties and applications. Chem Soc Rev 2012, 41:7108-7146.
• [3]Carriazo D, Serrano MC, Gutiérrez MC, Ferrer ML, del Monte F: Deep eutectic solvents playing multiple roles in the synthesis of polymers and related materials. Chem Soc Rev 2012, 41:4996-5014.
• [4]Maugeri Z, Domínguez de María P: Novel choline chloride based deep eutectic solvents with renewable hydrogen bond donors: levulinic acid and sugar-based polyols. RSC Adv 2012, 2:421-425.
• [5]Domínguez de María P, Maugeri Z: Ionic Liquids in biotransformations: from proof-of-concept to deep eutectic solvents. Curr Opin Chem Biol 2011, 15:220-225.
• [6]Gill I, Vulfson E: Enzymic catalysis in heterogeneous eutectic mixtures of substrates. Trends Biotech. 1994, 12:118-122.
• [7]Smith EL, Abbott AP, Ryder KS: Deep eutectic solvents and their applications. Chem Rev 2014, 114:11060-11082.
• [8]Maugeri Z, Leitner W, Domínguez de María P: Practical separation of alcohol-ester mixtures using deep-eutectic-solvents. Tetrahedron Lett 2012, 53:6968-6971.
• [9]Krystof M, Pérez-Sánchez M, Domínguez de María P: Lipase-catalyzed (trans)esterification of 5-hydroxymethylfurfural and separation of HMF-esters using deep eutectic-solvents. Chem Sus Chem 2013, 6:630-634.
• [10]Groeger H, Hummel W: Combining the “two worlds” of chemocatalysis and biocatalysis towards multi-step one-pot processes in aqueous media. Curr Opin Chems Biol 2014, 19:171-179.
• [11]Heidlindemann M, Rully G, Berkessel A, Hummel W, Groeger H: Combination of asymmetric organo- and biocatalytic reactions in organic media using immobilized catalysts in diferente compartments. ACS Catal 2014, 4:1099-1103.
• [12]Majumder AB, Ramesh NG, Gupta MN: A lipase catalysed condensation reaction with a tricyclic diketone: yet another example of biocatalytic promiscuity. Tetrahedron Lett 2009, 50:5190-5193.
• [13]Mueller CR, Meiners I, Domínguez de María P: Highly enantioselective tandem enzyme-organocatalyst crossed aldol reactions with acetaldehyde in deep eutectic solvents. RSC Adv 2014, 4:46097-46101.
• [14]Lin Q, Meloni D, Pan Y, Mia M, Rodgers J, Shepard S, et al.: Enantioselective synthesis of Janus Kinase inhibitor INCB018424 via an organocatalytic Aza-Michael reaction. Org Lett 2009, 11:1999-2002.
• [15]Pace V, Hoyos P, Castoldi L, Domínguez de María P, Alcántara AR: 2-methyltetrahydrofuran (2-MeTHF): A biomass-derived solvent with broad application in organic chemistry. Chem Sus Chem 2012, 5:1369-1379.
• [16]Pickering L, Malhi BS, Coe PL, Walker RT: 4′-Methyloxycarbamyl-3′-deoxy-5-methyluridine; synthesis of a novel nucleoside analogue. Tetrahedron 1995, 51:2719-2728.
• [17]Alza E, Sayalero S, Kasaplar P, Almasi D, Pericas MA: Polystyrene supported diarylprolinol ethers as highly efficient organocatalysts for Michael-type reactions. Chem Eur J 2011, 17:11585-11595.
• [18]Maltsev OV, Kucherenko AS, Chimishkyan AL, Zlotin SG: α, α-Diarylprolinol-derived chiral ionic liquids: recoverable organocatalysts for the domino reaction between α, β-enals and N-protected hydroxylamines. Tetrahedron Asymmetry 2010, 21:2659-2670.
• [19]Itoh T, Ishikawa H, Hayashi Y: Asymmetric Aldol reaction of acetaldehyde and isatin derivatives for the total syntheses of ent-convolutamydine E and CPC-1 and a half fragment of madindoline A and B. Org Lett 2009, 11:3854-3857.