EP1758878A1 - Procede de production de 4-(alpha-hydroxyalkyl)-1,3-dioxan-5-ones - Google Patents

Procede de production de 4-(alpha-hydroxyalkyl)-1,3-dioxan-5-ones

Info

Publication number
EP1758878A1
EP1758878A1 EP05753902A EP05753902A EP1758878A1 EP 1758878 A1 EP1758878 A1 EP 1758878A1 EP 05753902 A EP05753902 A EP 05753902A EP 05753902 A EP05753902 A EP 05753902A EP 1758878 A1 EP1758878 A1 EP 1758878A1
Authority
EP
European Patent Office
Prior art keywords
aryl
substituted
compounds
independently
unsubstituted alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05753902A
Other languages
German (de)
English (en)
Inventor
Bernhard Westermann
Meinolf Lange
Nasir Hayat
Christiane Neuhaus
Fritz Link
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Girindus AG
Original Assignee
Girindus AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Girindus AG filed Critical Girindus AG
Priority to EP05753902A priority Critical patent/EP1758878A1/fr
Publication of EP1758878A1 publication Critical patent/EP1758878A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings

Definitions

  • the present invention relates to a synthesis process and compounds obtainable thereby.
  • Aldol reactions are one of the essential carbon / carbon linking reactions both in nature and in the repertoire of the synthetic chemist. In nature, such reactions are catalyzed by enzymes that function either via an enamine mechanism (class 1 aldolases) or via a zinc cofactor (class 2 aldolases). Here a high stereoselectivity is achieved.
  • Marek Majewski et al. describe in J. Org. Chem. 65 (2000) 5152-5160 a process for the aldol reaction of enolates starting from 1,3-dioxan-5-ones by reaction with chiral lithium amides.
  • R substituted or unsubstituted alkyl, aryl, heterocycles containing one or more O, N, S, P or B;
  • Ri and R 2 independently of one another are H, substituted or unsubstituted alkyl, Aryl, heterocycles containing one or more O, N, S, P or B
  • R ' H, OH, OR or OSiX 3 where X are independently alkyl or aryl.
  • a cyclic starting compound namely derivatives of 1,3-dioxan-5-one, is used, which are reacted with aldehydes in the presence of proline or proline derivatives.
  • These starting compounds are dihydroxyacetone derivatives. High stereoselectivities are achieved.
  • proline or proline derivative forms an enamine intermediate, in which the carboxy group of the proline is involved in the orientation, so that the surprisingly high stereoselectivities are achieved.
  • Alkyl in the sense of this application are in particular straight-chain or branched alkyl, cycloalkyl, bicycloalkyl, tricycloalkyl, alkenyl, alkynyl, heterocycloalkyl compounds. Typical representatives are methyl, ethyl, N-propyl, isopropyl, butyl, cyclohexyl or substituted derivatives thereof.
  • Aryl in the sense of this application also includes, in particular, heteroaryl, arylalkyl or heteroarylalkyl groups. Typical representatives are phenyl, benzyl, pyrridine and substituted derivatives thereof.
  • the alkyl or aryl radicals can also be substituted by one or more hydroxy, alkoxy, aryloxy, alkanoyl, aroyl, carboxy, alkoxycarbonyl, amino, alkylamino, hydroxylamino, amido, carbamoyl , Ureido, amidino, guanidino, cyano, azido, mercapto, alkylthio, alkylsulfoxy, alkylsulfonyl, alkylsulfonyl, aminosulfonyl, fluorine, chlorine, bromine, iodine, alkyl or perfluoroalkyl radicals substituted derivatives.
  • R contains one or more nitrogen atoms.
  • nitrogen atoms are derivatives of compounds with, for example, azididine, pyrrolidine, pyrroline, piperidine, piperazine, homopiperazine, morpholine, thiomorpholine, pyridine, di- or tetra-hydropyridine, pyrimidine, Pyrazine, azepine, dihydroazepine, oxazepine, diazepine, imidazole, pyrazole, oxazole or Thiazole rings, which may have fused-on aliphatic, heteroaliphatic, aromatic or heteroaromatic rings and / or by one or more hydroxy, alkoxy, aryloxy, aklanoyl, aroyl, carboxy, alkoxycarbonyl, amino, alkylamino -, Hydroxylamino, amido, carbanoyl, ureido, amidino, guanidino, cyano, azido
  • the amounts of proline or proline derivative required for the reaction are typically 0.1 to 30 mol%, more preferably 1 to 10 mol%, even more preferably 1 to 5 mol%.
  • proline or proline derivative used only catalytically participates in the reaction and can therefore in principle be recovered.
  • reaction is carried out using L-proline.
  • D-proline is typically used to obtain the compounds 2, 4.
  • 4-hydroxyproline or a protected precursor thereof can also be used.
  • the ratio of the formation of anti (1, 2) or syn (2, ⁇ 4) compounds depends on the component of structural formula 6.
  • the reaction is carried out in an aqueous solvent.
  • the proportion of water is then preferably more than 50% and even more preferably more than 90%.
  • reaction is carried out without a solvent.
  • Particularly suitable solvents are trifluoroethanol and formamide, both optionally mixed with water.
  • the water content is preferably below 20%.
  • Other suitable solvents are DMSO and DMF. Mixtures of these solvents can of course also be used.
  • radicals R are those in which R is -CH (OH) -CH 2 -N 3 (R or S) or 6
  • the invention further relates to the use of compound 5 as a reagent for an aldol reaction.
  • the invention further relates to compounds of the general formula
  • R substituted or unsubstituted alkyl, aryl, heterocycles containing one or more O, N, S, P or B;
  • Ri and R 2 are independently H, substituted or unsubstituted alkyl, aryl, heterocycles containing one or more O, N, S, P or B.
  • the substances according to the invention which can be obtained in high stereoselectivities on the new synthetic route, are particularly suitable as starting or intermediate products in the synthesis of carbohydrates and aza-carbohydrates. Therefore the use of the compound according to the invention as an intermediate in the synthesis of carbohydrates or Aza carbohydrates Subject of the invention.
  • the dihydroxyacetone backbone is recovered. If necessary, this can enter into ring closure reactions coupled with the rest coupled through the aldol reactions. In embodiments in which R contains an amine, this can be used to form aza sugars or amino sugars.
  • L-proline produced both the anti and the syn product. They could be separated chromatographically and showed the following NMR spectroscopy data.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de synthèse de composés des formules générales (1), (2), (3), (4). Ce procédé consiste à faire réagir les formules (5) et (6) en présence de la formule de (7) où R représente alkyle, aryle substitué ou non substitué, des hétérocycles contenant au moins O, N, S, P, B; R1 et R2 représentent indépendamment l'un de l'autre H, alkyle, aryle substitué ou non substitué, des hétérocycles contenant au moins O, N, S, P ou B ; R' représente H, OH, OR ou OSiX3, X représentant indépendamment alkyle ou aryle.
EP05753902A 2004-06-15 2005-06-15 Procede de production de 4-(alpha-hydroxyalkyl)-1,3-dioxan-5-ones Withdrawn EP1758878A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05753902A EP1758878A1 (fr) 2004-06-15 2005-06-15 Procede de production de 4-(alpha-hydroxyalkyl)-1,3-dioxan-5-ones

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04102730A EP1609787A1 (fr) 2004-06-15 2004-06-15 Procede de production de 4-(alpha-hydroxyalkyl)-1,3-dioxan-5-ones
PCT/EP2005/052757 WO2005123712A1 (fr) 2004-06-15 2005-06-15 Procede de production de 4-(alpha-hydroxylalkyle)-1,3-dioxan-5-ones
EP05753902A EP1758878A1 (fr) 2004-06-15 2005-06-15 Procede de production de 4-(alpha-hydroxyalkyl)-1,3-dioxan-5-ones

Publications (1)

Publication Number Publication Date
EP1758878A1 true EP1758878A1 (fr) 2007-03-07

Family

ID=34929204

Family Applications (2)

Application Number Title Priority Date Filing Date
EP04102730A Withdrawn EP1609787A1 (fr) 2004-06-15 2004-06-15 Procede de production de 4-(alpha-hydroxyalkyl)-1,3-dioxan-5-ones
EP05753902A Withdrawn EP1758878A1 (fr) 2004-06-15 2005-06-15 Procede de production de 4-(alpha-hydroxyalkyl)-1,3-dioxan-5-ones

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP04102730A Withdrawn EP1609787A1 (fr) 2004-06-15 2004-06-15 Procede de production de 4-(alpha-hydroxyalkyl)-1,3-dioxan-5-ones

Country Status (3)

Country Link
US (1) US7851639B2 (fr)
EP (2) EP1609787A1 (fr)
WO (1) WO2005123712A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8789135B1 (en) * 2012-06-15 2014-07-22 Google Inc. Scalable stateful firewall design in openflow based networks
US10829482B2 (en) 2016-12-27 2020-11-10 Kao Corporation Method for producing glyceric acid ester
WO2018124147A1 (fr) 2016-12-27 2018-07-05 花王株式会社 Procédé de fabrication 1,3-dioxane-5-ones
WO2018124148A1 (fr) 2016-12-27 2018-07-05 花王株式会社 Procédé de fabrication d'ester d'acide glycérique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005123712A1 *

Also Published As

Publication number Publication date
US20080097113A1 (en) 2008-04-24
EP1609787A1 (fr) 2005-12-28
WO2005123712A1 (fr) 2005-12-29
US7851639B2 (en) 2010-12-14

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