Facile evolution of asymmetric organocatalysts in water assisted by surfactant brønsted acids

Abstract Simple mixing of chiral amines and surfactant Bronsted acids such as p-dodecyl benzenesulfonic acid (DBSA) leads to highly effective and selective organocatalysts in water. The in situ generated catalysts catalyze highly stereoselective desymmetrization of prochiral ketones via direct aldol reactions (up to >16:1 dr, >99% ee) in water using micelle as reaction media. The current strategy was also applied in asymmetric Michael addition leading to a catalytic system with good activity and stereoselectivity.

[1]  S. Shirakawa,et al.  Surfactant-type Brønsted acid catalyzed dehydrative nucleophilic substitutions of alcohols in water. , 2007, Organic letters.

[2]  K N Houk,et al.  Quantum mechanical predictions of the stereoselectivities of proline-catalyzed asymmetric intermolecular aldol reactions. , 2003, Journal of the American Chemical Society.

[3]  Y. Hayashi,et al.  Cysteine-derived organocatalyst in a highly enantioselective intramolecular Michael reaction. , 2005, Journal of the American Chemical Society.

[4]  Reactions in micellar systems. , 2005, Angewandte Chemie.

[5]  T. Rovis,et al.  Asymmetric synthesis of hydrobenzofuranones via desymmetrization of cyclohexadienones using the intramolecular Stetter reaction. , 2006, Journal of the American Chemical Society.

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

[7]  L. Gong,et al.  Small peptides catalyze highly enantioselective direct aldol reactions of aldehydes with hydroxyacetone: unprecedented regiocontrol in aqueous media. , 2004, Organic letters.

[8]  Shuj Kobayashi,et al.  Dehydration reactions in water. Brønsted Acid-surfactant-combined catalyst for ester, ether, thioether, and dithioacetal formation in water. , 2002, Journal of the American Chemical Society.

[9]  J. Háfren,et al.  The small peptide-catalyzed direct asymmetric aldol reaction in water. , 2006, Organic & biomolecular chemistry.

[10]  D. MacMillan,et al.  Modern strategies in organic catalysis: The advent and development of iminium activation , 2006 .

[11]  Ulf M Lindström,et al.  Stereoselective organic reactions in water. , 2002, Chemical reviews.

[12]  Yi-Ju Cao,et al.  Michael additions in water of ketones to nitroolefins catalyzed by readily tunable and bifunctional pyrrolidine–thiourea organocatalysts , 2007 .

[13]  Tsubasa Okano,et al.  Combined proline-surfactant organocatalyst for the highly diastereo- and enantioselective aqueous direct cross-aldol reaction of aldehydes. , 2006 .

[14]  S. S. Chimni,et al.  Small organic molecule catalyzed enantioselective direct aldol reaction in water , 2006 .

[15]  B. Trost,et al.  Asymmetric transition-metal-catalyzed allylic alkylations: applications in total synthesis. , 2003, Chemical reviews.

[16]  Shaowu Wang,et al.  Highly efficient and reusable dendritic catalysts derived from N-prolylsulfonamide for the asymmetric direct aldol reaction in water. , 2006, Organic letters.

[17]  C. Barbas,et al.  Amino acid catalyzed direct asymmetric aldol reactions: a bioorganic approach to catalytic asymmetric carbon-carbon bond-forming reactions. , 2001, Journal of the American Chemical Society.

[18]  S. Shirakawa,et al.  Carboxylic acid catalyzed three-component aza-Friedel-Crafts reactions in water for the synthesis of 3-substituted indoles. , 2006, Organic letters.

[19]  X. Cui,et al.  Design of highly enantioselective organocatalysts based on molecular recognition. , 2006, Organic letters.

[20]  V. Singh,et al.  Highly enantioselective water-compatible organocatalyst for Michael reaction of ketones to nitroolefins. , 2007, Organic letters.

[21]  Y. Hayashi.  In water or in the presence of water? , 2006, Angewandte Chemie.

[22]  P. Pihko,et al.  Effect of additives on the proline-catalyzed ketone-aldehyde aldol reactions , 2006 .

[23]  S. Luo,et al.  Surfactant-type asymmetric organocatalyst: organocatalytic asymmetric Michael addition to nitrostyrenes in water. , 2006, Chemical communications.

[24]  I. Alfonso,et al.  Enantioselective enzymatic desymmetrizations in organic synthesis. , 2005, Chemical reviews.

[25]  B. List.  The ying and yang of asymmetric aminocatalysis. , 2006, Chemical communications.

[26]  Tsubasa Okano,et al.  Dry and wet prolines for asymmetric organic solvent-free aldehyde-aldehyde and aldehyde-ketone aldol reactions. , 2007, Chemical communications.

[27]  K. Manabe,et al.  Development of novel Lewis acid catalysts for selective organic reactions in aqueous media. , 2002, Accounts of chemical research.

[28]  C. Barbas,et al.  Direct organocatalytic asymmetric Mannich-type reactions in aqueous media: one-pot Mannich-allylation reactions , 2003 .

[29]  S. Bandyopadhyay,et al.  Water Exclusion and Enantioselectivity in Catalysis , 2006, Chembiochem : a European journal of chemical biology.

[30]  W. Zhuang,et al.  Organocatalytic asymmetric epoxidation reactions in water-alcohol solutions. , 2005, Organic & biomolecular chemistry.

[31]  K. Janda,et al.  Enamine-based aldol organocatalysis in water: are they really "all wet"? , 2006, Angewandte Chemie.

[32]  F. Tanaka,et al.  Organocatalytic direct michael reaction of ketones and aldehydes with beta-nitrostyrene in brine. , 2006, Journal of the American Chemical Society.

[33]  S. S. Chimni,et al.  Protonated chiral prolinamide catalyzed enantioselective direct aldol reaction in water , 2005 .

[34]  C. Jimeno,et al.  Polystyrene-supported hydroxyproline: an insoluble, recyclable organocatalyst for the asymmetric aldol reaction in water. , 2006, Organic letters.

[35]  Y. Hayashi,et al.  Highly diastereo- and enantioselective direct aldol reactions in water. , 2006, Angewandte Chemie.

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

[37]  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.

[38]  C. Barbas,et al.  Direct amino acid-catalyzed asymmetric desymmetrization of meso-compounds: tandem aminoxylation/O-N bond heterolysis reactions. , 2005, Organic letters.

[39]  J. Reymond,et al.  Catalytic, Enantioselective Aldol Reaction with an Artificial Aldolase Assembled from a Primary Amine and an Antibody , 1995 .

[40]  Yixin Lu,et al.  Asymmetric aldol reactions catalyzed by tryptophan in water. , 2006, Chemical communications.

[41]  Jun Jiang,et al.  Enantioselective desymmetrization of prochiral cyclohexanone derivatives via the organocatalytic direct Aldol reaction. , 2007, Chemical communications.

[42]  Hisashi Yamamoto,et al.  Design of acid-base catalysis for the asymmetric direct Aldol reaction. , 2004, Accounts of chemical research.

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

[44]  W. Shao,et al.  Studies on Direct Stereoselective Aldol Reactions in Aqueous Media , 2004 .

[45]  Chao-Jun Li,et al.  Organic reactions in aqueous media with a focus on carbon-carbon bond formations: a decade update. , 2005, Chemical reviews.

[46]  K. Janda,et al.  Aqueous aldol catalysis by a nicotine metabolite. , 2002, Journal of the American Chemical Society.

[47]  Jian Wang,et al.  A recyclable fluorous (S)-pyrrolidine sulfonamide promoted direct, highly enantioselective Michael addition of ketones and aldehydes to nitroolefins in water. , 2006, Organic letters.

[48]  L. Gong,et al.  Organocatalyzed highly enantioselective direct aldol reactions of aldehydes with hydroxyacetone and fluoroacetone in aqueous media: the use of water to control regioselectivity. , 2007, Chemistry.

[49]  P. Dalko,et al.  In the golden age of organocatalysis. , 2004, Angewandte Chemie.

[50]  C. Barbas,et al.  Amine-catalyzed direct self Diels–Alder reactions of α,β-unsaturated ketones in water: synthesis of pro-chiral cyclohexanones , 2002 .

[51]  G. Celentano,et al.  Enantioselective direct aldol reaction "on water" promoted by chiral organic catalysts. , 2007, Organic letters.

[52]  Shuj Kobayashi,et al.  Mannich-type reactions in water using a hydrophobic polymer-supported sulfonic acid catalyst , 2003 .