Chitosan Aerogel Beads as a Heterogeneous Organocatalyst for the Asymmetric Aldol Reaction in the Presence of Water: An Assessment of the Effect of Additives

The catalytic properties of chitosan aerogel for the direct asymmetric aldol reaction in water assisted by various surfactants and acid co-catalysts have been evaluated by employing a range of donor and acceptor systems. A beneficial effect on both the yields and nantioselectivities was observed, and the combination of surfactants and acid co-catalysts has proven particularly useful in the case of heterocyclic ketone donors.

[1]  K. Manabe,et al.  Catalytic asymmetric hydroxymethylation of silicon enolates using an aqueous solution of formaldehyde with a chiral scandium complex. , 2004, Journal of the American Chemical Society.

[2]  B. Krajewska,et al.  Chitosan as a lipid binder: a langmuir monolayer study of chitosan-lipid interactions. , 2007, Biomacromolecules.

[3]  J. Paradowska,et al.  Direct asymmetric α-hydroxymethylation of ketones in homogeneous aqueous solvents , 2010 .

[4]  F. Quignard,et al.  Chitosan aerogel: a recyclable, heterogeneous organocatalyst for the asymmetric direct aldol reaction in water. , 2010, Chemical communications.

[5]  S. Denmark,et al.  Chiral Phosphoramide-Catalyzed Aldol Additions of Ketone Enolates. Preparative Aspects , 1999 .

[6]  S. Doherty,et al.  Oxazoline-substituted prolinamide-based organocatalysts for the direct intermolecular aldol reaction between cyclohexanone and aromatic aldehydes , 2008 .

[7]  J. Devoisselle,et al.  Porous chitosan-silica hybrid microspheres as a potential catalyst , 2004 .

[8]  L. Janssen,et al.  Kinetics and chemical equilibrium of the hydration of formaldehyde , 2002 .

[9]  D. Plusquellec,et al.  Aqueous solutions of facial amphiphilic carbohydrates as sustainable media for organocatalyzed direct aldol reactions , 2012 .

[10]  L. Bernardi,et al.  Organocatalysis in the Asymmetric Synthesis of Nitrogen-Containing Compounds: How and Why , 2007 .

[11]  E. Guibal.  Heterogeneous catalysis on chitosan-based materials: a review , 2005 .

[12]  Runtao Li,et al.  Aldol reaction catalyzed by a hydrophilic catalyst in aqueous micelle as an enzyme mimic system. , 2009, Chirality.

[13]  L. Lay,et al.  Novel carbohydrate-based bifunctional organocatalysts for nucleophilic addition to nitroolefins and imines. , 2011, Organic & biomolecular chemistry.

[14]  F. Quignard,et al.  Supercritical CO2 dried chitosan: an efficient intrinsic heterogeneous catalyst in fine chemistry , 2003 .

[15]  F. Quignard,et al.  From natural polysaccharides to materials for catalysis, adsorption, and remediation. , 2010, Topics in current chemistry.

[16]  G. Guillena,et al.  High acceleration of the direct aldol reaction cocatalyzed by BINAM-prolinamides and benzoic acid in aqueous media , 2006 .

[17]  Franco Cozzi.  Immobilization of Organic Catalysts: When, Why, and How , 2006 .

[18]  W. Xiao,et al.  Sterically and electronically tunable and bifunctional organocatalysts: design and application in asymmetric aldol reaction of cyclic ketones with aldehydes. , 2006, The Journal of organic chemistry.

[19]  F. Quignard,et al.  Palladium supported on chitosan hollow fiber for nitrotoluene hydrogenation , 2009 .

[20]  F. Quignard,et al.  Marine polysaccharides and their conversion into functional materials. , 2011, Chimia.

[21]  F. Quignard,et al.  Chitosan supported phthalocyanine complexes: Bifunctional catalysts with basic and oxidation active sites , 2006 .

[22]  F. Quignard,et al.  Polysaccharides: Natural Polymeric Supports for Aqueous Phase Catalysts in the Allylic Substitution Reaction , 2002 .

[23]  Jeffrey J. E. Hardy,et al.  Applications of Functionalized Chitosan in Catalysis , 2005 .

[24]  Water in Stereoselective Organocatalytic Reactions , 2009 .

[25]  Dennis Kuehbeck,et al.  Critical assessment of the efficiency of chitosan biohydrogel beads as recyclable and heterogeneous organocatalyst for C–C bond formation , 2012 .

[26]  T. Kristensen,et al.  Polymer-Supported Chiral Organocatalysts: Synthetic Strategies for the Road Towards Affordable Polymeric Immobilization , 2010 .

[27]  Chao Pi,et al.  Simple amphiphilic isosteviol–proline conjugates as chiral catalysts for the direct asymmetric aldol reaction in the presence of water , 2010 .

[28]  Kelly M Shields,et al.  Chitosan for weight loss and cholesterol management. , 2003, American journal of health-system pharmacy : AJHP : official journal of the American Society of Health-System Pharmacists.

[29]  F. Renzo,et al.  Aerogel materials from marine polysaccharides , 2008 .

[30]  D. Alonso,et al.  Prolinamides versus Prolinethioamides as Recyclable Catalysts in the Enantioselective Solvent-Free Inter-and Intramolecular Aldol Reactions , 2008 .

[31]  H. Kunz,et al.  Enantioselective Organocatalysis of Strecker and Mannich Reactions Based on Carbohydrates , 2007 .

[32]  S. Ley,et al.  Organocatalysis with proline derivatives: improved catalysts for the asymmetric Mannich, nitro-Michael and aldol reactions. , 2005, Organic & biomolecular chemistry.

[33]  C. Barbas,et al.  Direct organocatalytic aldol reactions in buffered aqueous media. , 2002, Chemical communications.

[34]  D. Gryko,et al.  Brønsted acids as additives for the direct asymmetric aldol reaction catalyzed by l-prolinethioamides. direct evidence for enamine-iminium catalysis. , 2007, The Journal of organic chemistry.

[35]  F. Tanaka,et al.  Rapid fluorescent screening for bifunctional amine-acid catalysts: efficient syntheses of quaternary carbon-containing aldols under organocatalysis. , 2003, Organic Letters.

[36]  P. Wang,et al.  Proline catalyzed aldol reactions in aqueous micelles: an environmentally friendly reaction system , 2003 .

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

[38]  M. Raj,et al.  Organocatalytic reactions in water. , 2009, Chemical communications.

[39]  D. MacMillan,et al.  The advent and development of organocatalysis , 2008, Nature.

[40]  D. E. Ward,et al.  Proline-catalyzed asymmetric aldol reactions of tetrahydro-4H-thiopyran-4-one with aldehydes , 2004 .

[41]  M. Comes Franchini,et al.  Bioinspired organocatalytic asymmetric reactions. , 2012, Organic & biomolecular chemistry.

[42]  M. Kantam,et al.  Chitosan hydrogel : A green and recyclable biopolymer catalyst for aldol and knoevenagel reactions , 2006 .

[43]  Xiaomei Zhang,et al.  A simple and eco-friendly method for the aminomethylation of 3-substituted oxindoles via three-component Mannich reaction in aqueous media , 2011 .

[44]  M. Umar,et al.  Picolylamine as an organocatalyst template for highly diastereo- and enantioselective aqueous aldol reactions. , 2010, Organic & biomolecular chemistry.

[45]  D. Deng,et al.  Stereoselective aldol reactions catalyzed by acyclic amino acids in aqueous micelles , 2007 .