Direct anti-markovnikov addition of acids to alkenes

Patent metadata

Field	Value
Publication number	US-10017441-B2
Application number	US-201414787179-A
Country	US
Kind code	B2
Filing date	May 2, 2014
Priority date	May 2, 2013
Publication date	Jul 10, 2018
Grant date	Jul 10, 2018

Abstract

A method of making an anti-Markovnikov addition product, comprises reacting an acid with an alkene or alkyne in a dual catalyst reaction system to the exclusion of oxygen to produce said anti-Markovnikov addition product; the dual catalyst reaction system comprising a single electron oxidation catalyst in combination with a hydrogen atom donor catalyst. Dual catalyst composition useful for carrying out such methods are also described.

First claim

That which is claimed is:

1. A method of making an anti-Markovnikov addition product, comprising:
reacting an acid with an Acne or alkyne in a dual catalyst reaction system to the exclusion of oxygen to produce said anti-Markovnikov addition product;
said dual catalyst reaction system comprising a single electron oxidation catalyst in combination with a hydrogen atom donor catalyst, wherein said single electron oxidation catalyst is a ground state oxidation catalyst;
wherein said hydrogen atom donor catalyst is a compound of the Formula A-SH, where A is alkyl, aryl, or an electron withdrawing group.

2. The method of claim 1 , wherein said anti-Markovnikov addition product is produced regioselectively in a ratio of at least 5:1 of anti-Markovnikov addition product to Markovnikov addition product.

3. The method of claim 1 , wherein A is selected from the group consisting of alkyl, aryl, carboxyl, and carbonyl groups.

4. The method of claim 1 , wherein said single electron oxidation catalyst is a photocatalyst.

5. The method of claim 4 , wherein said photocatalyst comprises a carbocyclic or heterocyclic aromatic compound containing ring nitrogen heteroatoms.

6. The method of claim 5 , wherein said photocatalyst comprises an anthracene, aza-anthracene or polyaza-anthracene nucleus which is unsubstituted, substituted or polysubstituted at any position with halogen, and/or with one or more lower alkyl or cycloalkyl radicals, and/or with other phenyl substituents.

7. The method of claim 4 , wherein said photocatalyst has a reduction potential of about −1.0 V to +0.1 V against a saturated calomel reference electrode in 100 percent acetonitrile as determined by cyclic voltammetry.

8. The method of claim 1 , wherein said ground state oxidation catalyst is selected from the group consisting of eerie ammonium nitrate, ferrocenium tetrafluoroberate, nitrosyl tetrafluoroborate, iron trichloride, iron (III) tris(phenanthroline) tris(hexafluorophosphate), and tris(4-bromopheny)aminium hexafluoroantimonate.

9. The method of claim , wherein said reaction system is free of transition metal catalysts.

10. The method of claim 1 , wherein said reacting is an intramolecular hydroalkoxylation reaction.

11. The method of claim 1 , wherein said reacting is an intramolecular hydrolactonization reaction.

12. The method of claim 1 , wherein said reacting is an intermolecular hydroacetoxylation reaction.

13. The method of claim 1 , wherein said reacting is an anti-Markovnikov polymerization reaction where the acid and alkene group are contained within the same monomeric unit or are contained on separate monomeric units.

Assignees

• Univ North Carolina Chapel Hill

Inventors

• Nicewicz David A
• Hamilton David S

Classifications

• B01J2231/324

  Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions · CPC title

• C07D325/00

  Heterocyclic compounds containing rings having oxygen as the only ring hetero atom according to more than one of groups C07D303/00 - C07D323/00 · CPC title

• C07B37/02

  Addition · CPC title

• B01J35/004

  Operations & Transport · mapped topic

• C07D291/06

  Six-membered rings · CPC title