Direct, enantioselective aldol coupling of aldehydes using...

Details Direct, enantioselective aldol coupling of aldehydes using... Direct, enantioselective aldol coupling of aldehydes using...

2005-04-21

2009-06-02

Jiang, Shaojia Anna (Department: 1623)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carbohydrates or derivatives

Reexamination Certificate

active

07541456

ABSTRACT:
Nonmetallic, chiral organic catalysts are used to catalyze an enantioselective aldol coupling reaction between aldehyde substrates. The reaction may be carried out with a single enolizable aldehyde, resulting in dimerization to give a β-hydroxy aldehyde, or trimerization to give a dihydroxy tetrahydropyran. The reaction may also conducted with an enolizable aldehyde and a second aldehyde, which may or may not be enolizable, so that the coupling is a cross-aldol reaction in which the α-carbon of the enolizable aldehyde adds to the carbonyl carbon of the second aldehyde in an enantioselective fashion. Reaction systems composed of at least one enolizable aldehyde, an optional additional aldehyde, and the nonmetallic chiral organic catalyst are also provided, as are methods of implementing the enantioselective aldol reaction in the synthesis of sugars.

REFERENCES:
patent: 4324884 (1982-04-01), White et al.
patent: 4355184 (1982-10-01), Kaku et al.
patent: 4528405 (1985-07-01), Papa
patent: 5428174 (1995-06-01), Reissenweber et al.
patent: 5430194 (1995-07-01), Barner et al.
patent: 5786373 (1998-07-01), Hartman et al.
patent: 5977290 (1999-11-01), Siebenhaar
patent: 6040262 (2000-03-01), Fougret et al.
patent: 6307057 (2001-10-01), MacMillan et al.
patent: 6369243 (2002-04-01), MacMillan et al.
patent: WO 92/02505 (1992-02-01), None
patent: WO 96/31615 (1996-10-01), None
patent: WO 03/047740 (2003-06-01), None
Ahrendt et al. (2000), “New Strategies for Organic Catalysis: The First Highly Enantioselective Organocatalytic Diels—Alder Reaction,”J. Am. Chem. Soc. 122(17):4243-4244.
Evans et al. (1997), “ChiralC2-Symmetric Cu(II) Complexes as Catalysis for Enantioselective Intramolecular Diels-Alder Reactions. Asymmetric Synthesis of (−)-Isopulo'upone,”J. Org. Chem. 62(4):786-787.
Frederickson (1997), “Opitcally Active IsoxazolidinesviaAsymmetric Cycloaddition Reactions of Nitrones with Alkenes: Applications in Organic Synthesis,”Tetrahedron53(2):403-425.
Ishihara et al. (1996), “A New Powerful and Practical BLA Catalyst for Highly-Enantioselective Diels-Alder Reations: An Extreme Acceleration of Reaction Rate by Brønsted Acid,”J. Am. Chem. Soc. 118(12):3049-3050.
Iwasawa et al. (1989), “Asymmetric Intramolecular Diels-Alder Reaction Catalyzed by the Chiral Titanium Reagent,”Chemistry Letters, pp. 1947-1950.
Jen et al. (2000), “New Strategies for Organic Catalysis: The First Enantioselective Organocatalytic 1,3-Dipolar Cycloaddition,”J. Am. Chem. Soc. 122(40):9874-9875.
Jensen et al. (2001), “Catalytic Asymmetric Friedel-Crafts Alkylation of β,γ-Unsaturated α-Ketoesters: Enantioselective Addition of Aromatic C-H Bonds to Alkenes,”Angew. Chem. Int. Edit. 40(1):160-163.
Johannsen (1999), “An Enantioselective Synthesis of HeteroaromaticN-Tosyl α-Amino Acids,”Chem. Commun., pp. 2233-2234.
Maruoka et al. (1994), “Virtually Complete Blocking of α,β-Unsaturated Aldehyde Carbonyls by Complexation with Aluminum Tris(2,6-diphenylphenoxide),”J. Am. Chem. Soc. 116(9):4131-4132.
Northrup et al. (2002), “The First Direct and Enantioselective Cross-Aldol Reaction of Aldehydes,” J. Am. Chem. Soc. Supporting Information, Northrup ja0262378, pp. S1-S7.
Ohta et al. (1996), “Novel 5-Hydroxytryptamine (5-HT3) Receptor Antagonists. III. Pharmacological Evaluations and Molecular Modeling Studies of Optically Active 4,5,6,7-Tetrahydro-1H-Benzimidazole Derivatives,”Chem. Pharm. Bull. 44(9):1707-1716.
Paras et al. (2001), “New Strategies in Organic Catalysis: The First Enantioseelective Organocatalytic Friedel—Crafts Alkylation,”J. Am. Chem. Soc. 123(18):4370-4371.
Schuster et al. (2000), “Catalysis of a Diels—Alder Reaction by Amidinium Ions,” J. Org. Chem. 65:1697-1701.
Shi et al. (1995), “Synthesis of Axially Dissymmetric Chiral Ammonium Salts by Quaternization of Secondary Amines with (R)-(+)-2,2′-Bis(bromomethyl)-6,6′-dinitrobiphenyl and (R)-(+)-2,2′-Bis(bromomethyl)-1,1′-binaphthyl and an Examination of Their Abilities as Chiral Phase-Transfer Catalysts,”J. Chem. Research(S), pp. 46-47 (J. Chem. Research(M), pp. 0401-0411).
Solodin et al. (1990), “(5S)-5-Benzyl-2,2,3-trimethylimidazolidin-4-one as a Highly Effective Chiral Auxiliary for Asymmetric Reduction of α-Oxo Amides,”J. Chem. Soc., Chem. Commun., pp. 1321-1322.
Yang et al. (1998), “Design and Synthesis of Chiral Ketones for Catalytic Asymmetric Epoxidation of Unfunctionalized Olefins,”J. Am. Chem. Soc. 120(24):5943-5952.
Supplementary European Search Report, Feb. 27, 2007, EPO.
Notz et al. (2000), “Catalytic Asymmetric Synthesis of Anti-1,2 Diols,”J. Am. Chem. Soc., 122, 7386-7387.
Cordova et al. (2002), “A highly enantioselective route to either enantiomer of both alpa- and beta- amino acid derivatives,”J. Am. Chem. Soc., 124, 1866-1867.
List B. et al. (2000), “Proline-Catalyzed Direct Asymmetric Aldol Reactions,”J. Am. Chem. Soc., 122, 2395-2396.
Gijsen H.J.M. et al. (1995), “Sequential Three-and Four-Substrate Aldol Reactions Catalyzed by Aldolases,”J. Am. Chem. Soc., 117, 7585-7591.
Northrup A.B. et al. (2002), “The first Direct and Enantioselective Cross-Aldol Reaction of Aldehydes,”J. Am. Chem. Soc., 124, 6798-6799.
Chowdari N.S. et al. (2002), “Proline-Catalyzed Asymmetric Assembly Reactions: Enzyme-Like Assembly of Carbohydrates and Polyketides from Three Aldehyde Substrates,”Tetrahedron Letters., 43, 9591-9595.
Chen et al. (1992), “Deoxyribose-5-phosphate Aldolase as a Catalyst in Asymmetric Aldol Reaction,”J. Am. Chem. Soc., 114, 741-748.
Barbas et al. (1990), “Deoxyribose-5-phosphate Aldolase as a Synthetic Catalyst,”J. Am. Chem. Soc., 112, 2013-2014.
Wong et al. (1995), “Recombinant 2-Deoxyribose-5-phosphate Aldolase in Organic Synthesis: Use of Sequencial Two-Substrate and Three-Substrate Aldol Reactions,”J. Am. Chem. Soc., 117, 3333-3339.
Machajewski et al. (2000), “The Catalytic Asymmetric Aldol Reaction,”Angewandte Chemie Int'l Ed. in English, 39, 1353-1374.

Affiliated with

Also associated with

Rating

Direct, enantioselective aldol coupling of aldehydes using... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Direct, enantioselective aldol coupling of aldehydes using..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Direct, enantioselective aldol coupling of aldehydes using... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-4087430