Recent Advances in Asymmetric Catalysis in Flow

Asymmetric catalysis in flow has been attracting much attention very recently because of the potential advantages over its batchwise counterpart, such as high-throughput screening and synthesis, easy automation with the integration of on-demand reaction analysis, little or no reaction workup, and potential long-term use of the catalysts in the case of heterogeneous catalysis. Homogeneous asymmetric catalysis performed in a microreactor has demonstrated successful examples in fast catalyst screening, integrated inline/onlineanalysis, microflow photocatalysis, multistep transformation with unstable intermediates, and potential for lower catalyst loading or homogeneous catalyst recylcing. Since heterogeneous asymmetric catalysis serves as a better way than its homogeneous analogue for catalyst separation and recycling, this Review Article summarizes recent development via different catalyst immobilization methods, such as covalent support, a self-supported method, an adsorption method, and H-bonding, electro...

[1]  Wolfgang Ehrfeld,et al.  Microreactors: New Technology for Modern Chemistry , 2000 .

[2]  K. Hult,et al.  High-throughput synthesis and analysis of acylated cyanohydrins. , 2007, Chemistry.

[3]  J. Yoshida,et al.  Asymmetric carbolithiation of conjugated enynes: a flow microreactor enables the use of configurationally unstable intermediates before they epimerize. , 2011, Journal of the American Chemical Society.

[4]  S. Haswell,et al.  Asymmetric Catalysis in a Micro Reactor : Ce, Yb and Lu Catalysed Enantioselective Addition of Trimethylsilyl Cyanide to Benzaldehyde , 2004 .

[5]  Miquel A. Pericàs,et al.  Fast and Enantioselective Production of 1‐Aryl‐1‐propanols through a Single Pass, Continuous Flow Process , 2008 .

[6]  Thomas Lectka,et al.  Sequential column asymmetric catalysis. , 2002, Chemistry.

[7]  M. Lautens,et al.  New frontiers in asymmetric catalysis , 2007 .

[8]  S. Mukherjee,et al.  Asymmetric enamine catalysis. , 2007, Chemical reviews.

[9]  M. Rueping,et al.  Continuous-flow catalytic asymmetric hydrogenations: Reaction optimization using FTIR inline analysis , 2012, Beilstein journal of organic chemistry.

[10]  Michael Oelgemoeller,et al.  Highlights of Photochemical Reactions in Microflow Reactors , 2012 .

[11]  Hiroyuki Nakamura,et al.  Integrated microreaction system for optical resolution of racemic amino acids. , 2007, Lab on a chip.

[12]  Helmut Pennemann,et al.  Asymmetric catalytic hydrogenations at micro-litre scale in a helicoidal single channel falling film micro-reactor , 2005 .

[13]  Victor Sans,et al.  Residence time distribution, a simple tool to understand the behaviour of polymeric mini-flow reactors , 2012 .

[14]  Andreas Kirschning,et al.  Ten key issues in modern flow chemistry. , 2011, Chemical communications.

[15]  J. L. Irwin,et al.  Towards a continuous dynamic kinetic resolution of 1-phenylethylamine using a membrane assisted, two vessel process. , 2007, Chemical communications.

[16]  W. Stark,et al.  Cu(II)−Azabis(oxazoline) Complexes Immobilized on Magnetic Co/C Nanoparticles: Kinetic Resolution of 1,2-Diphenylethane-1,2-diol under Batch and Continuous-Flow Conditions , 2010 .

[17]  T. Wirth,et al.  Asymmetric reactions in flow reactors , 2011 .

[18]  Kazunori Watanabe,et al.  High-efficiency and minimum-waste continuous kinetic resolution of racemic alcohols by using lipase in supercritical carbon dioxide. , 2004, Chemical communications.

[19]  Kazunori Watanabe,et al.  Biocatalytic reduction of ketones by a semi-continuous flow process using supercritical carbon dioxide. , 2003, Chemical communications.

[20]  T. Wirth,et al.  Microreactors in organic synthesis and catalysis , 2008 .

[21]  P. Licence,et al.  Continuous Asymmetric Hydrogenation in Supercritical Carbon Dioxide using an Immobilised Homogeneous Catalyst , 2006 .

[22]  Li Peng,et al.  Solid Acids as Heterogeneous Support for Primary Amino Acid‐Derived Diamines in Direct Asymmetric Aldol Reactions , 2011 .

[23]  Santiago V. Luis,et al.  Chemical reactions and processes under flow conditions , 2009 .

[24]  T. Lectka,et al.  Asymmetric catalysis on sequentially-linked columns. , 2001, Journal of the American Chemical Society.

[25]  Thomas Lectka,et al.  Performing the synthesis of a complex molecule on sequentially linked columns: toward the development of a "synthesis machine". , 2005, Organic letters.

[26]  Victor Sans,et al.  Stereoselective Chemoenzymatic Synthesis of Enantiopure 2-(1H-imidazol-yl)cycloalkanols under Continuous Flow Conditions , 2012 .

[27]  Peter H Seeberger,et al.  Continuous-flow synthesis of the anti-malaria drug artemisinin. , 2012, Angewandte Chemie.

[28]  M. A. Pericàs,et al.  Polystyrene-supported (2S)-(-)-3-exo-piperazinoisoborneol: an efficient catalyst for the batch and continuous flow production of enantiopure alcohols. , 2012, Organic letters.

[29]  D. Popa,et al.  Towards Continuous Flow, Highly Enantioselective Allylic Amination: Ligand Design, Optimization and Supporting , 2009 .

[30]  Detlev Belder,et al.  Asymmetric organocatalysis and analysis on a single microfluidic nanospray chip. , 2011, Angewandte Chemie.

[31]  Peter H. Seeberger,et al.  Organic synthesis: Scavengers in full flow. , 2009, Nature chemistry.

[32]  Detlev Belder,et al.  Enantioselective catalysis and analysis on a chip. , 2006, Angewandte Chemie.

[33]  J. Fréchet,et al.  New solid-phase catalysts for asymmetric synthesis: cross-linked polymers containing a chiral Schiff base-zinc complex , 1990 .

[34]  Paul Watts,et al.  Recent advances in micro reaction technology. , 2011, Chemical communications.

[35]  J. Iborra,et al.  A Continuous Reactor for the (Chemo)enzymatic Dynamic Kinetic Resolution of Rac-1-Phenylethanol in Ionic Liquid/Supercritical Carbon Dioxide Biphasic Systems , 2007 .

[36]  Jun-ichi Yoshida,et al.  Flash Chemistry: Fast Organic Synthesis in Microsystems , 2008 .

[37]  J. Mayoral,et al.  Pybox monolithic miniflow reactors for continuous asymmetric cyclopropanation reaction under conventional and supercritical conditions. , 2007, The Journal of organic chemistry.

[38]  W. Leitner,et al.  A Versatile Lab to Pilot Scale Continuous Reaction System for Supercritical Fluid Processing , 2011 .

[39]  Dong‐Pyo Kim,et al.  Triple-channel microreactor for biphasic gas–liquid reactions: Photosensitized oxygenations , 2011, Beilstein journal of organic chemistry.

[40]  P. Seeberger,et al.  5-(Pyrrolidin-2-yl)tetrazole-catalyzed aldol and mannich reactions: acceleration and lower catalyst loading in a continuous-flow reactor. , 2009, Angewandte Chemie.

[41]  K. Schöning,et al.  Immobilized biocatalysts in industrial research and production. , 2004, Topics in current chemistry.

[42]  Volker Hessel,et al.  Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry , 2009 .

[43]  Ryan L. Hartman,et al.  Deciding whether to go with the flow: evaluating the merits of flow reactors for synthesis. , 2011, Angewandte Chemie.

[44]  D. T. McQuade,et al.  Continuous proline catalysis via leaching of solid proline , 2011, Beilstein journal of organic chemistry.

[45]  Tadashi Suzuki,et al.  Asymmetric photosensitized addition of methanol to (R)-(+)-(Z)-limonene in a microreactor , 2007 .

[46]  Jonathan P. McMullen,et al.  Rapid Determination of Reaction Kinetics with an Automated Microfluidic System , 2011 .

[47]  Nathalie Tanchoux,et al.  Microreactors for Dynamic, High Throughput Screening of Fluid/Liquid Molecular Catalysis , 2000 .

[48]  Steven V. Ley,et al.  The Changing Face of Organic Synthesis , 2008 .

[49]  Steven V Ley,et al.  Organic synthesis in a changing world. , 2002, Chemical record.

[50]  D. Murzin,et al.  Asymmetric Heterogeneous Catalysis: Science and Engineering , 2005 .

[51]  Volker Hessel,et al.  Potential Analysis of Smart Flow Processing and Micro Process Technology for Fastening Process Development: Use of Chemistry and Process Design as Intensification Fields , 2012 .

[52]  M. A. Pericàs,et al.  Asymmetric α‐Amination of Aldehydes Catalyzed by PS‐Diphenylprolinol Silyl Ethers: Remediation of Catalyst Deactivation for Continuous Flow Operation , 2012 .

[53]  R. Souza,et al.  Towards a continuous flow environment for lipase-catalyzed reactions , 2013 .

[54]  W. Leitner,et al.  Continuous Enantioselective Hydrogenation with a Molecular Catalyst in Supported Ionic Liquid Phase under Supercritical CO2 Flow , 2010 .

[55]  J. Bakos,et al.  A Continuous-Flow System for Asymmetric Hydrogenation Using Supported Chiral Catalysts , 2011 .

[56]  Alfons Baiker,et al.  Ionic liquids and dense carbon dioxide: a beneficial biphasic system for catalysis. , 2011, Chemical reviews.

[57]  A. Mandoli,et al.  Insoluble polystyrene-bound bis(oxazoline): batch and continuous-flow heterogeneous enantioselective glyoxylate–ene reaction , 2004 .

[58]  Rafael Luque,et al.  Magnetically recoverable nanocatalysts. , 2011, Chemical reviews.

[59]  S. Kee,et al.  Batch versus continuous mg-scale synthesis of chalcone epoxide with soluble polyethylene glycol poly-L-leucine catalyst. , 2007 .

[60]  Flavien Susanne,et al.  Continuous flow synthesis. A pharma perspective. , 2012, Journal of medicinal chemistry.

[61]  T. Tsubogo,et al.  Toward efficient asymmetric carbon-carbon bond formation: continuous flow with chiral heterogeneous catalysts. , 2012, Chemistry.

[62]  Christopher G. Frost,et al.  Heterogeneous catalytic synthesis using microreactor technology , 2010 .

[63]  Zheng Wang,et al.  Self-supported catalysts. , 2009, Chemical reviews.

[64]  A. Manz,et al.  Miniaturized total chemical analysis systems: A novel concept for chemical sensing , 1990 .

[65]  I. Mándity,et al.  Asymmetric aldol reaction in a continuous-flow reactor catalyzed by a highly reusable heterogeneous peptide , 2012 .

[66]  Neil R Thomas,et al.  Biocatalysis in supercritical fluids, in fluorous solvents, and under solvent-free conditions. , 2007, Chemical reviews.

[67]  F. Bonfils,et al.  Michael reactions carried out using a bench-top flow system. , 2006, Organic & biomolecular chemistry.

[68]  Timothy F. Jamison,et al.  Continuous flow multi-step organic synthesis , 2010 .

[69]  C. Bellefon,et al.  Micro-structured reactors as a tool for chiral modifier screening in gas-liquid-solid asymmetric hydrogenations , 2007 .

[70]  R. Haag,et al.  Continuous Application of Polyglycerol‐Supported Salen in a Membrane Reactor: Asymmetric Epoxidation of 6‐Cyano‐2,2‐dimethylchromene , 2008 .

[71]  Diána Weiser,et al.  How the mode of Candida antarctica lipase B immobilization affects the continuous-flow kinetic resolution of racemic amines at various temperatures , 2013 .

[72]  Norbert Kockmann,et al.  Harsh Reaction Conditions in Continuous‐Flow Microreactors for Pharmaceutical Production , 2009 .

[73]  E. García‐Verdugo,et al.  Supported Ionic Liquid-Like Phases (SILLPs) for enzymatic processes: Continuous KR and DKR in SILLP–scCO2 systems , 2010 .

[74]  J. Reek,et al.  Reverse-flow adsorption for process-integrated recycling of homogeneous transition-metal catalysts. , 2011, Chemistry.

[75]  Z. Wang,et al.  Self-supported chiral catalysts for heterogeneous enantioselective reactions , 2006, Chemistry.

[76]  T. Lectka,et al.  A column-based ‘flush and flow’ system for the asymmetric α-chlorination of acid halides , 2005 .

[77]  Zheng Wang,et al.  Development of a continuous-flow system for asymmetric hydrogenation using self-supported chiral catalysts. , 2009, Chemistry.

[78]  J. Reek,et al.  Solid-phase synthesis of homogeneous ruthenium catalysts on silica for the continuous asymmetric transfer hydrogenation reaction. , 2001, Chemistry.

[79]  A. Henseler,et al.  A solid-supported organocatalyst for continuous-flow enantioselective aldol reactions. , 2012, ChemSusChem.

[80]  J. Bakos,et al.  Asymmetric hydrogenation of CC double bonds using Rh-complex under homogeneous, heterogeneous and continuous mode conditions , 2012 .

[81]  R. Müller,et al.  Kinetic resolution of 2-chloro-3,3,3-trifluoropropanoic acid esters catalyzed by lipase from Candida rugosa , 2011 .

[82]  Andreas Liese,et al.  Coupled chemo(enzymatic) reactions in continuous flow , 2011, Beilstein journal of organic chemistry.

[83]  Markus Hager,et al.  Application of metal-based reagents and catalysts in microstructured flow devices. , 2012, ChemSusChem.

[84]  I. Mándity,et al.  Highly efficient 1,4-addition of aldehydes to nitroolefins: organocatalysis in continuous flow by solid-supported peptidic catalysts. , 2012, ChemSusChem.

[85]  Dongbo Zhao Updated Applications of Flow Chemistry in Pharmaceutical Synthesis , 2013 .

[86]  J C M van Hest,et al.  Enzymatic enantioselective C-C-bond formation in microreactors. , 2008, Biotechnology and bioengineering.

[87]  T. Lectka,et al.  Column Asymmetric Catalysis for β-Lactam Synthesis , 2000 .

[88]  Peter H Seeberger,et al.  Asymmetric reactions in continuous flow , 2009, Beilstein journal of organic chemistry.

[89]  E. García‐Verdugo,et al.  Efficient and selective chemical transformations under flow conditions: The combination of supported catalysts and supercritical fluids , 2011, Beilstein journal of organic chemistry.

[90]  F. Kaspersen Chirality in Industry. The Commercial Manufacture and Applications of Optically Active Compounds. A.N. Collins, G.N. Sheldrake, J. Crosby eds., John Wiley, Chichester, 1992 ix + 409 pp., £65.00. ISBN 0-471-935956 , 2010 .

[91]  J. Mayoral,et al.  Efficient enhancement of copper-pyridineoxazoline catalysts through immobilization and process design , 2011 .

[92]  Philip Hodge,et al.  Organic synthesis using polymer-supported reagents, catalysts and scavengers in simple laboratory flow systems. , 2003, Current opinion in chemical biology.

[93]  Steven J. Broadwater,et al.  The continuous-flow synthesis of Ibuprofen. , 2009, Angewandte Chemie.

[94]  J. Wegner,et al.  Flow Chemistry – A Key Enabling Technology for (Multistep) Organic Synthesis , 2012 .

[95]  Neal G. Anderson,et al.  Using Continuous Processes to Increase Production , 2012 .

[96]  E. García‐Verdugo,et al.  Bioreactors based on monolith-supported ionic liquid phase for enzyme catalysis in supercritical carbon dioxide , 2007 .

[97]  C. Santini,et al.  Supported ionic liquid phase catalysis with supercritical flow. , 2007, Chemical communications.

[98]  K. Zeitler,et al.  Application of microflow conditions to visible light photoredox catalysis. , 2012, Organic letters.

[99]  J. Mayoral,et al.  Polymer-Supported Bis(oxazolines) and Related Systems: Toward New Heterogeneous Enantioselective Catalysts , 2005 .

[100]  Alan Armstrong,et al.  The flow's the thing..or is it? Assessing the merits of homogeneous reactions in flask and flow. , 2010, Angewandte Chemie.

[101]  Santiago V. Luis,et al.  (Bio)Catalytic Continuous Flow Processes in scCO2 and/or ILs: Towards Sustainable (Bio)Catalytic Synthetic Platforms , 2011 .

[102]  Steven V. Ley,et al.  Asymmetric Homogeneous Hydrogenation in Flow using a Tube-in-Tube Reactor , 2012 .

[103]  J. Gladysz Introduction: recoverable catalysts and reagents-perspective and prospective. , 2002, Chemical reviews.

[104]  T. Hiyama,et al.  Solvent-free asymmetric olefin hydroformylation catalyzed by highly cross-linked polystyrene-supported (R,S)-BINAPHOS-Rh(I) complex. , 2003, Journal of the American Chemical Society.

[105]  Pedro M. P. Gois,et al.  Recyclable stereoselective catalysts. , 2009, Chemical reviews.

[106]  M. Garland,et al.  Self-supported chiral titanium cluster (SCTC) as a robust catalyst for the asymmetric cyanation of imines under batch and continuous flow at room temperature. , 2012, Chemistry.

[107]  Kerstin Würges,et al.  Continuous Biocatalytic Processes , 2009 .

[108]  D. Wenn,et al.  Gas-liquid and gas-liquid-solid catalysis in a mesh microreactor. , 2004, Chemical communications.

[109]  L. Dai Chiral metal-organic assemblies--a new approach to immobilizing homogeneous asymmetric catalysts. , 2004, Angewandte Chemie.

[110]  P. Hodge,et al.  Asymmetric synthesis of 1-phenylpropanol using polymer-supported chiral catalysts in simple bench-top flow systems† , 1999 .

[111]  Timothy Noël,et al.  Suzuki-Miyaura cross-coupling reactions in flow: multistep synthesis enabled by a microfluidic extraction. , 2011, Angewandte Chemie.

[112]  Lara Babich,et al.  Synthesis of carbohydrates in a continuous flow reactor by immobilized phosphatase and aldolase. , 2012, ChemSusChem.

[113]  J. Mayoral,et al.  Bisoxazoline-functionalised enantioselective monolithic mini-flow-reactors: development of efficient processes from batch to flow conditions , 2007 .

[114]  N. Shimada,et al.  Continuous flow system with a polymer-supported dirhodium(II) catalyst: application to enantioselective carbonyl ylide cycloaddition reactions. , 2011, Chemistry.

[115]  J. Rolland,et al.  Continuous flow enantioselective arylation of aldehydes with ArZnEt using triarylboroxins as the ultimate source of aryl groups , 2009, Beilstein journal of organic chemistry.

[116]  S. Buchwald,et al.  Enantioselective β-arylation of ketones enabled by lithiation/borylation/1,4-addition sequence under flow conditions. , 2012, Angewandte Chemie.

[117]  N. Mahata,et al.  Anchored homogeneous catalysts: the role of the heteropoly acid anchoring agent , 2003 .

[118]  Volker Hessel,et al.  High Throughput Kinetic Investigations of Asymmetric Hydrogenations with Microdevices , 2003 .

[119]  S. Itsuno Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis: Itsuno/Polymeric Chiral Catalyst , 2011 .

[120]  M. Vicent,et al.  New supported beta-amino alcohols as efficient catalysts for the enantioselective addition of diethylzinc to benzaldehyde under flow conditions. , 2002, Organic letters.

[121]  K. Ding,et al.  Handbook of Asymmetric Heterogeneous Catalysis , 2008 .

[122]  Timothy Noël,et al.  Cross-coupling in flow. , 2011, Chemical Society reviews.

[123]  S. Tagawa,et al.  The Intramolecular Electron Transfer between the Type 1 Cu and the Type 2 Cu in a Mutant of Hyphomicrobium Nitrite Reductase , 2005 .

[124]  M. Islam,et al.  Nanoflow microreactor for dramatic increase not only in reactivity but also in selectivity: Baeyer–Villiger oxidation by aqueous hydrogen peroxide using lowest concentration of a fluorous lanthanide catalyst , 2006 .

[125]  Y. Asano,et al.  Homogeneous Enantioselective Catalysis in a Continuous-Flow Microreactor: Highly Enantioselective Borohydride Reduction of Ketones Catalyzed by Optically Active Cobalt Complexes , 2012 .

[126]  M. A. Pericàs,et al.  Continuous-flow enantioselective α-aminoxylation of aldehydes catalyzed by a polystyrene-immobilized hydroxyproline , 2011, Beilstein journal of organic chemistry.

[127]  W. Leitner,et al.  Mechanistic aspects of dihydrogen activation and transfer during asymmetric hydrogenation in supercritical carbon dioxide. , 2000, Chirality.