Direct asymmetric aldol reaction of 5H-oxazol-4-ones with aldehydes catalyzed by chiral guanidines.

A new chiral bicyclic guanidine-catalyzed direct catalytic aldol reaction of 5H-oxazol-4-ones with aldehydes has been developed. The present aldol reaction proceeds smoothly with high enantioselectivity using bicyclic guanidines bearing a hydroxy group at the appropriate position, and various combinations of 5H-oxazol-4-ones and aldehydes are applicable. The method provides synthetically useful alpha,beta-dihydroxycarboxylates bearing a chiral quaternary stereogenic center at the alpha-carbon atom.

[1]  Yuta Suzuki,et al.  Direct catalytic asymmetric aldol reactions of thioamides: toward a stereocontrolled synthesis of 1,3-polyols. , 2009, Journal of the American Chemical Society.

[2]  B. Trost,et al.  Evaluating transition-metal-catalyzed transformations for the synthesis of laulimalide. , 2009, Journal of the American Chemical Society.

[3]  S. Matsunaga,et al.  Construction of contiguous tetrasubstituted chiral carbon stereocenters via direct catalytic asymmetric aldol reaction of alpha-isothiocyanato esters with ketones. , 2009, Journal of the American Chemical Society.

[4]  Natalie C. Giampietro,et al.  Asymmetric tandem wittig rearrangement/Aldol reactions. , 2009, Journal of the American Chemical Society.

[5]  S. Matsunaga,et al.  Catalytic asymmetric synthesis of alpha-alkylidene-beta-hydroxy esters via dynamic kinetic asymmetric transformation involving Ba-catalyzed direct aldol reaction. , 2009, Journal of the American Chemical Society.

[6]  Choon‐Hong Tan,et al.  Synthesis of a chiral quaternary carbon center bearing a fluorine atom: enantio- and diastereoselective guanidine-catalyzed addition of fluorocarbon nucleophiles. , 2009, Angewandte Chemie.

[7]  Choon‐Hong Tan,et al.  Chiral guanidine catalyzed enantioselective reactions. , 2009, Chemistry, an Asian journal.

[8]  M. Terada,et al.  Enantioselective direct aldol-type reaction of azlactone via protonation of vinyl ethers by a chiral Brønsted acid catalyst. , 2009, Journal of the American Chemical Society.

[9]  B. Trost,et al.  Magnesium-catalyzed asymmetric direct aldol addition of ethyl diazoacetate to aromatic, aliphatic, and alpha,beta-unsaturated aldehydes. , 2009, Journal of the American Chemical Society.

[10]  Y. Hayashi,et al.  Diphenylprolinol silyl ether as a catalyst in an enantioselective, catalytic michael reaction for the formation of alpha,alpha-disubstituted alpha-amino acid derivatives. , 2009, Chemistry, an Asian journal.

[11]  J. Mccarthy,et al.  Mitsunobu approach to the synthesis of optically active alpha,alpha-disubstituted amino acids. , 2009, Organic letters.

[12]  D. Uraguchi,et al.  Chiral tetraaminophosphonium carboxylate-catalyzed direct Mannich-type reaction. , 2008, Journal of the American Chemical Society.

[13]  Le Li,et al.  Catalytic enantioselective aldol additions of alpha-isothiocyanato imides to aldehydes. , 2008, Journal of the American Chemical Society.

[14]  C. Barbas,et al.  Towards organocatalytic polyketide synthases with diverse electrophile scope: trifluoroethyl thioesters as nucleophiles in organocatalytic Michael reactions and beyond. , 2008, Angewandte Chemie.

[15]  S. Denmark,et al.  Lewis base activation of Lewis acids: catalytic, enantioselective addition of glycolate-derived silyl ketene acetals to aldehydes. , 2008, The Journal of organic chemistry.

[16]  K. Nagasawa,et al.  Asymmetric organocatalytic nitroaldol reaction of α-ketoesters : stereoselective construction of chiral tertiary alcohols at subzero temperature , 2008 .

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

[18]  C. Bewley,et al.  Mirabamides A-D, depsipeptides from the sponge Siliquariaspongia mirabilis that inhibit HIV-1 fusion. , 2007, Journal of natural products.

[19]  S. Saito,et al.  Highly anti-selective catalytic aldol reactions of amides with aldehydes. , 2006, Journal of the American Chemical Society.

[20]  C. Grison,et al.  First stereoselective synthesis of potassium aeschynomate and its no-natural stereomers , 2006 .

[21]  Takuya Kumamoto,et al.  Guanidine‐Catalyzed Asymmetric Trimethylsilylcyanation of Carbonyl Compounds , 2005 .

[22]  M. Kameda,et al.  Development of highly diastereo- and enantioselective direct asymmetric aldol reaction of a glycinate Schiff base with aldehydes catalyzed by chiral quaternary ammonium salts. , 2004, Journal of the American Chemical Society.

[23]  B. Trost,et al.  5H-oxazol-4-ones as building blocks for asymmetric synthesis of alpha-hydroxycarboxylic acid derivatives. , 2004, Journal of the American Chemical Society.

[24]  Davidr . Evans,et al.  Ni(II) bis(oxazoline)-catalyzed enantioselective syn aldol reactions of N-propionylthiazolidinethiones in the presence of silyl triflates. , 2003, Journal of the American Chemical Society.

[25]  S. Matsunaga,et al.  Direct catalytic asymmetric Michael reaction of hydroxyketones: asymmetric Zn catalysis with a Et2Zn/linked-BINOL complex. , 2003, Journal of the American Chemical Society.

[26]  Susumu Kobayashi,et al.  Stereocontrolled preparation of 1,2-diol with quaternary chiral center , 2002 .

[27]  A. Guerrini,et al.  Synthesis and desilylation of (2R,3S)-α-methyl-α-silyl-α,β-2,3-dihydroxycarboxylic methyl esters , 2002 .

[28]  B. Trost,et al.  Asymmetric Aldol Reaction via a Dinuclear Zinc Catalyst: α-Hydroxyketones as Donors , 2001 .

[29]  E. Corey,et al.  Enantioselective synthesis of alpha-amino nitriles from N-benzhydryl imines and HCN with a chiral bicyclic guanidine as catalyst. , 1999, Organic letters.

[30]  H. Shao,et al.  Novel Enantioselective Synthesis of a-Methylthreonines and a,-Dimethylcysteines , 1998 .

[31]  S. Kobayashi,et al.  Chiral Lewis Acid Controlled Synthesis (CLAC Synthesis): Chiral Lewis Acids Influence the Reaction Course in Asymmetric Aldol Reactions for the Synthesis of Enantiomeric Dihydroxythioester Derivatives in the Presence of Chiral Diamines Derived from L‐Proline , 1997 .

[32]  M. Nambu,et al.  Enantiospecific synthesis of (+)- and (–)-trachelanthic acids via asymmetric dihydroxylation and their conversion to the pyrrolizidine alkaloids indicine and intermedine , 1996 .

[33]  Kevin J. Dempsey,et al.  Synthesis and investigation of a hindered, chiral, bicyclic guanidine , 1995 .

[34]  Isamu Shiina,et al.  An Efficient Method for the Preparation of Chiral Synthons Starting from Racemic Compounds by Way of Asymmetric Synthesis , 1992 .

[35]  M. Sawamura,et al.  Catalytic asymmetric aldol reaction: reaction of aldehydes with isocyanoacetate catalyzed by a chiral ferrocenylphosphine-gold(I) complex , 1986 .

[36]  Masahiro Suzuki,et al.  Enantioselective synthesis of (+)-citreoviral using asymmetric hydroxylation of tiglate esters , 1985 .

[37]  D. Seebach,et al.  (α-Alkylation of α-heterosubstituted carboxylic acids without racemization : EPC-syntheses of tertiary alcohols and thiols☆☆☆ , 1984 .

[38]  K. Wilson,et al.  Syntheses of macrolide antibiotics. II. Methymycin , 1975 .

[39]  Joyce M. Wright,et al.  Alternaric Acid, a Biologically Active Metabolic Product of the Fungus Alternaria Solani , 1949, Nature.