Amino polyols and amino sugars

• US 7,462,746 B2
• Filed: 04/01/2003
• Issued: 12/09/2008
• Est. Priority Date: 06/28/1996
• Status: Expired due to Fees

• Current Assignee: University of Southern California
• Original Assignee: University of Southern California
• Inventors: Petasis, Nicos A., Zavialov, Ilia A., Patel, Zubin D.
• Primary Examiner(s): SHIBUYA, MARK LANCE
• Application Number:
  US10/405,922
• Publication Number:
  US 20040053330A1
• Time in Patent Office: 2,079 Days
• Field of Search: 564/507, 564/463, 564/503, 564/506
• US Class Current: 564/507
• CPC Class Codes: B01J 2219/00738 Organic catalysts
• CPC Class Codes: B01J 2219/00745 Inorganic compounds
• CPC Class Codes: B01J 2219/00747 Catalysts
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 31/2409 with more than one complexing phosphine-P atom
• CPC Class Codes: C07B 2200/07 Optical isomers
• CPC Class Codes: C07B 53/00 Asymmetric syntheses
• CPC Class Codes: C07C 213/02 by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
• CPC Class Codes: C07C 215/28 and containing six-membered aromatic rings
• CPC Class Codes: C07C 215/30 containing hydroxy groups and carbon atoms of six-membered aromatic rings bound to the same carbon atom of the carbon skeleton
• CPC Class Codes: C07C 215/50 with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
• CPC Class Codes: C07C 227/10 with simultaneously increasing the number of carbon atoms in the carbon skeleton
• CPC Class Codes: C07C 229/36 with at least one amino group and one carboxyl group bound to the same carbon atom of the carbon skeleton
• CPC Class Codes: C07C 231/08 from amides by reaction at nitrogen atoms of carboxamide groups
• CPC Class Codes: C07C 233/47 having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
• CPC Class Codes: C07C 2603/74 Adamantanes
• CPC Class Codes: C07D 207/16 Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 295/15 to an acyclic saturated chain
• CPC Class Codes: C07D 307/52 Radicals substituted by nitrogen atoms not forming part of a nitro radical
• CPC Class Codes: C07D 333/16 by oxygen atoms
• CPC Class Codes: C07D 333/20 : by nitrogen atoms nitro, nitroso radicals C07D333/12
• CPC Class Codes: C07D 333/24 : Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 333/58 : Radicals substituted by nitrogen atoms
• CPC Class Codes: C07D 333/60 : Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07H 5/06 : Aminosugars
• CPC Class Codes: C40B 30/08 : by measuring catalytic activity
• CPC Class Codes: C40B 40/18 : Libraries containing only inorganic compounds or inorganic materials

Abstract

Synthetic methods provide for the simple, efficient preparation of amino polyols and derivatives. The methods include a three-component reaction of a carbohydrates with organoboron compounds and primary or secondary amine derivatives. The resulting amino polyols can be transformed into amino sugars. In one implementation, the amine moiety is protected, and an alkenyl, aryl or heteroaryl moiety is cleaved to form the amino sugar. Amino polyols and amino sugars prepared according to the methods are also described.

Claims

1. A compound of formula 4:

3. A method for preparing the amino polyol of claims 1 or 2, comprising:

providing a carbohydrate;

providing an amine;

providing an organoboron derivative; and

allowing the carbohydrate, amine and organoboron derivative to react to form an aminopolyol.

4. A method for preparing the amino polyol of claims 1 or 2, the method comprising providing a carbohydrate of formula 1a or 1b:

5. The method of claim 4, wherein the carbohydrate of formula 2, the amine of formula 2 or the organoboron compound of formula 3 is attached to a polymer or other solid support.

6. The method of claim 5, further comprising treating the aminopolyol product of formula 4 to form an amino sugar of formula 11a or 11b or formula 12a or 12b:

7. The method of claim 6, wherein treating the aminopolyol product includes forming a protected amine and treating the protected amine with a cleaving agent to generate a carbonyl group.

8. The method of claim 6, wherein one or more of R² or R³ is benzyl or substituted benzyl.

9. The method of claim 6, wherein the amine of formula 2 is 1,1-di(p-anisyl)methylamine.

10. The method of claim 6, wherein one or more of R² or R³ is allyl or substituted allyl.

11. The method of claim 6, wherein the amine of formula 2 is diallylamine.

12. The method of claim 4, further comprising treating the aminopolyol product of formula 4 to form an amino sugar of formula 11a or 11b or formula 12a or 12b;

13. The method of claim 12, wherein treating the aminopolyol product includes forming a protected amine and treating the protected amine with a cleaving agent to generate a carbonyl group.

14. The method of claim 12, wherein one or more of R² or R³ is benzyl or substituted benzyl.

15. The method of claim 12, wherein the amine of formula 2 is 1,1-di(p-anisyl)methylamine.

16. The method of claim 12, wherein one or more of R² or R³ is allyl or substituted allyl.

17. The method of claim 12, wherein the amine of formula 2 is diallylamine.

18. The method of claim 4, wherein the amino polyol is formed in predominantly one stereoisomer having the amino group in an anti-relationship to the adjacent hydroxyl group.

19. The method of claim 4, further comprising:

treating the amino polyol product to protect the amino group; and

oxidizing the polyol to generate a protected amino acid.

2. A compound of formula 4: