Recognition and activation by ureas and thioureas: stereoselective reactions using ureas and thioureas as hydrogen-bonding donors.

Hydrogen-bonding interaction plays a crucial role in the molecular recognition and activation processes of various biologically important reactions that are mediated by enzymes and antibodies in living organisms. Recently, it has been shown that a hydrogen-bonding donor can be used as a general acid catalyst for various types of reactions in organic chemistry. In this article, we describe enantioselective reactions catalyzed by urea and thiourea derivatives as general acid catalysts as well as diastereoselective reactions. This perspective provides an overview of this rapidly growing field.

[1]  A. Csámpai,et al.  Highly enantioselective conjugate addition of nitromethane to chalcones using bifunctional cinchona organocatalysts. , 2005, Organic letters.

[2]  P. Schreiner,et al.  H-bonding additives act like Lewis acid catalysts. , 2002, Organic letters.

[3]  F. Schmidtchen,et al.  Artificial Organic Host Molecules for Anions. , 1997, Chemical reviews.

[4]  William L. Jorgensen,et al.  Effects of hydration on the Claisen rearrangement of allyl vinyl ether from computer simulations , 1992 .

[5]  Mark S. Taylor,et al.  Highly enantioselective catalytic acyl-pictet-spengler reactions. , 2004, Journal of the American Chemical Society.

[6]  J. Lex,et al.  Highly efficient dynamic kinetic resolution of azlactones by urea-based bifunctional organocatalysts. , 2005, Angewandte Chemie.

[7]  E. Jacobsen,et al.  Asymmetric Catalytic Mannich Reactions Catalyzed by Urea Derivatives: Enantioselective Synthesis of β-Aryl-β-Amino Acids , 2002 .

[8]  Y. Takemoto,et al.  Bifunctional thiourea-catalyzed enantioselective double Michael reaction of γ,δ-unsaturated β-ketoester to nitroalkene: asymmetric synthesis of (−)-epibatidine , 2004 .

[9]  J. Lex,et al.  Second-generation organocatalysts for the highly enantioselective dynamic kinetic resolution of azlactones. , 2005, Chemical communications.

[10]  S. Takizawa,et al.  Bifunctional organocatalysts for enantioselective aza-Morita-Baylis-Hillman reaction. , 2005, Journal of the American Chemical Society.

[11]  E. Jacobsen,et al.  Thiourea-catalyzed enantioselective cyanosilylation of ketones. , 2005, Journal of the American Chemical Society.

[12]  T. R. Kelly,et al.  Diels-alder reactions: Rate acceleration promoted by a biphenylenediol , 1990 .

[13]  M. Sigman,et al.  A General Catalyst for the Asymmetric Strecker Reaction This work was supported by the NIH (GM-43214). A postdoctoral fellowship to M.S.S. (NIH), and a predoctoral fellowship to P.V. sponsored by Alfred Bader are gratefully acknowledged. , 2000, Angewandte Chemie.

[14]  A. D. Hamilton,et al.  Nitronate anion recognition and modulation of ambident reactivity by hydrogen-bonding receptors. , 2000, Chemistry.

[15]  D. Curran,et al.  Altering the Stereochemistry of Allylation Reactions of Cyclic .alpha.-Sulfinyl Radicals with Diarylureas , 1994 .

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

[17]  T. Ross Kelly,et al.  RELATIVE BINDING AFFINITY OF CARBOXYLATE AND ITS ISOSTERES : NITRO, PHOSPHATE, PHOSPHONATE, SULFONATE, AND DELTA -LACTONE , 1994 .

[18]  P. Schreiner,et al.  Metal-free, noncovalent catalysis of diels-alder reactions by neutral hydrogen bond donors in organic solvents and in water. , 2003, Chemistry.

[19]  Y. Takemoto,et al.  Enantioselective aza-Henry reaction catalyzed by a bifunctional organocatalyst. , 2004, Organic letters.

[20]  P. Váchal,et al.  Structure-based analysis and optimization of a highly enantioselective catalyst for the strecker reaction. , 2002, Journal of the American Chemical Society.

[21]  P. Váchal,et al.  Practical Synthesis of a Soluble Schiff Base Catalyst for the Asymmetric Strecker Reaction , 2001 .

[22]  Y. Takemoto,et al.  Enantioselective Michael Addition to α,β‐Unsaturated Imides Catalyzed by a Bifunctional Organocatalyst , 2005 .

[23]  P. Schreiner.  Metal-free organocatalysis through explicit hydrogen bonding interactions. , 2003, Chemical Society reviews.

[24]  M. Terada,et al.  Organocatalytic Asymmetric Direct Alkylation of α-Diazoester via C−H Bond Cleavage , 2005 .

[25]  Y. Takemoto,et al.  Enantio- and diastereoselective Michael reaction of 1,3-dicarbonyl compounds to nitroolefins catalyzed by a bifunctional thiourea. , 2005, Journal of the American Chemical Society.

[26]  C. Wilcox,et al.  Experimental and theoretical studies of substituent effects in hydrogen bond based molecular recognition of a zwitterion by substituted arylureas , 1995 .

[27]  Margaret C. Etter,et al.  Encoding and decoding hydrogen-bond patterns of organic compounds , 1990 .

[28]  P. Pihko.  Activation of carbonyl compounds by double hydrogen bonding: an emerging tool in asymmetric catalysis. , 2004, Angewandte Chemie.

[29]  S. Connon,et al.  Acceleration of the DABCO-promoted Baylis–Hillman reaction using a recoverable H-bonding organocatalyst ☆ , 2004 .

[30]  Y. Takemoto,et al.  Thiourea-catalyzed nucleophilic addition of TMSCN and ketene silyl acetals to nitrones and aldehydes , 2003 .

[31]  V. Rawal,et al.  Enantioselective Diels-Alder reactions catalyzed by hydrogen bonding. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[32]  L. Zani,et al.  Protonated chiral catalysts: versatile tools for asymmetric synthesis. , 2005, Angewandte Chemie.

[33]  S. Schaus,et al.  Asymmetric Morita-Baylis-Hillman reactions catalyzed by chiral Brønsted acids. , 2003, Journal of the American Chemical Society.

[34]  Y. Hashimoto,et al.  Development of bis-thiourea-type organocatalyst for asymmetric Baylis–Hillman reaction , 2004 .

[35]  Junji Itoh,et al.  Enantioselective Mannich-type reaction catalyzed by a chiral Brønsted acid. , 2004, Angewandte Chemie.

[36]  E. Jacobsen,et al.  Highly enantioselective thiourea-catalyzed nitro-Mannich reactions. , 2005, Angewandte Chemie.

[37]  D. Curran,et al.  Acceleration of a dipolar Claisen rearrangement by Hydrogen bonding to a soluble diaryl^urea , 1995 .

[38]  Y. Hashimoto,et al.  Development of novel chiral urea catalysts for the hetero-Michael reaction. , 2004, Chemical & pharmaceutical bulletin.

[39]  G. Joly,et al.  Thiourea-catalyzed enantioselective hydrophosphonylation of imines: practical access to enantiomerically enriched alpha-amino phosphonic acids. , 2004, Journal of the American Chemical Society.

[40]  J. N. Johnston,et al.  Chiral proton catalysis: a catalytic enantioselective direct aza-Henry reaction. , 2004, Journal of the American Chemical Society.

[41]  Hisashi Yamamoto,et al.  Bronsted acid catalysis of achiral enamine for regio- and enantioselective nitroso aldol synthesis. , 2005, Journal of the American Chemical Society.

[42]  William L. Jorgensen,et al.  Solvent effects on a Diels-Alder reaction from computer simulations , 1991 .

[43]  Margaret C. Etter,et al.  Hydrogen bond-directed cocrystallization and molecular recognition properties of diarylureas , 1990 .

[44]  P. Váchal,et al.  Enantioselective catalytic addition of HCN to ketoimines. Catalytic synthesis of quaternary amino acids. , 2000, Organic letters.

[45]  Y. Takemoto,et al.  Enantioselective Michael reaction of malonates to nitroolefins catalyzed by bifunctional organocatalysts. , 2003, Journal of the American Chemical Society.

[46]  Eric N. Jacobsen,et al.  SCHIFF BASE CATALYSTS FOR THE ASYMMETRIC STRECKER REACTION IDENTIFIED AND OPTIMIZED FROM PARALLEL SYNTHETIC LIBRARIES , 1998 .