Synthesis and application of chiral substituted polyvinylpyrrolidinones

Patent metadata

Field	Value
Publication number	US-10906033-B2
Application number	US-201716089609-A
Country	US
Kind code	B2
Filing date	Mar 28, 2017
Priority date	Mar 28, 2016
Publication date	Feb 2, 2021
Grant date	Feb 2, 2021

Abstract

Chiral polyvinylpyrrolidinone (CSPVP), complexes of CSPVP with a core species, such as a metallic nanocluster catalyst, and enantioselective oxidation reactions utilizing such complexes are disclosed. The CSPVP complexes can be used in asymmetric oxidation of diols, enantioselective oxidation of alkenes, and carbon-carbon bond forming reactions, for example. The CSPVP can also be complexed with biomolecules such as proteins, DNA, and RNA, and used as nanocarriers for siRNA or dsRNA delivery.

First claim

I claim:

1. A chiral substituted polyvinylpyrrolidinone compound having the formula

wherein one of R 1 and R 2 comprises a functional group having at least 1 carbon atom selected from the group consisting of alcohols, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, and combinations thereof, and the other of R 1 and R 2 is H or OH, and n is greater than 100.

2. The compound of claim 1 , wherein R 1 is selected from the group consisting of CH 2 Ph, CH 2 O-t-Bu, CHCH 3 CH 3 , CH 2 (1-Naph), CH 2 OH, CH 2 OCHPh 2 , and CH 2 OCH(o-Me-C 6 H 4 ) 2 , or R 2 is selected from the group consisting of OR′ (where R′ is an ester or alkyl group), CH 3 , an alkyl group, CH 2 OH, and the other of R 1 and R 2 is H or OH, and n is greater than 250.

3. The compound of claim 1 , wherein said compound has a molecular weight of at least 50,000.

4. A chiral substituted polyvinylpyrrolidinone compound comprising an acetonide moiety attached to the pyrrolidine ring.

5. The compound of claim 4 , wherein said compound has the formula

wherein each of R 1 and R 2 is independently selected from aliphatic or aromatic functional groups, and n is greater than 100.

6. A complex comprising the chiral substituted polyvinylpyrrolidinone compound of claim 1 bound to a core species selected from the group consisting of nanoparticulate materials, proteins, DNA, siRNA, and dsRNA.

7. The complex of claim 6 , wherein the complex comprises a nanoparticle cluster.

8. The complex of claim 7 , wherein the nanoparticle cluster comprises one or more metals.

9. The complex of claim 8 , wherein the nanoparticle cluster comprises one or more metals selected from the group consisting of Au, Pd, Cu, Ce, Mo, Ni, Ru, W, and Fe.

10. The complex of claim 8 , wherein the nanoparticle cluster is bimetallic.

11. The complex of claim 6 , wherein the bimetallic nanoparticle cluster is selected from the group consisting of Pd/Au, Cu/Au, Ce/Au, Mo/Au, W/Au, Ru/Au, and Fe/Au.

12. The complex of claim 6 , wherein the chiral substituted polyvinylpyrrolidinone compound encapsulates the core species.

13. A process for asymmetrically oxidizing organic molecules comprising reacting the organic molecule with one or more reagents in the presence of a complex comprising the chiral substituted polyvinylpyrrolidinone compound of claim 1 bound to a metallic nanocluster to produce chiral molecules.

14. The process of claim 13 , wherein the reaction results in the formation of a carbon-carbon bond with the formation of chiral organic molecules.

15. The process of claim 13 , wherein the organic molecule is an alkene, the reaction resulting in the oxidation of a carbon-carbon double bond producing chiral diols.

16. The process of claim 13 , wherein the organic molecule is selected from the group consisting of cis and trans 1,2-diols and 1,3-diols, the reaction resulting in the oxidation of one hydroxyl group of the organic molecule thereby producing a chiral hydroxyl ketone molecule.

17. The process of claim 13 , wherein the reaction oxidizes a carbon-hydrogen bond in the organic molecule to form a chiral alcohol or ketone molecule possessing a hydroxyl or carbonyl functional group.

18. The process of claim 13 , wherein the reaction generates a reaction product comprising two enantiomers, and wherein the enantiomeric excess of one of the enantiomers is greater than 50%.

19. The process of claim 13 , wherein the reaction generates a reaction product that is enantiopure.

20. The process of claim 13 , wherein the reaction generates a reaction product having a hydroxyl or ketone functional group, and wherein the reaction product is further reacted with an organic compound in which the organic compound is added to the reaction product at the site of the hydroxyl or ketone functional group.

21. The process of claim 13 , wherein the nanoparticle cluster comprises one or more metals selected from the group consisting of Au, Pd, Cu, Ce, Mo, Ni, Ru, W, and Fe.

22. The process of claim 21 , wherein the nanoparticle cluster is bimetallic.

23. The complex of claim 22 , wherein the bimetallic nanoparticle cluster is selected from the group consisting of Pd/Au, Cu/Au, Ce/Au, Mo/Au, Ni/Au, W/Au, Ru/Au, and Fe/Au.

Assignees

• Univ Kansas State

Inventors

• Hua Duy H

Classifications

• B01J2231/763

  of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species · CPC title

• C07D209/96

  Spiro-condensed ring systems · CPC title

• C07D209/80

  [b, c]- or [b, d]-condensed · CPC title

• C08F26/10

  N-Vinyl-pyrrolidone · CPC title

• B01J23/52

  Gold · CPC title