Alpha-hydrogen substituted nitroxyls and derivatives thereof as catalysts

Patent metadata

Field	Value
Publication number	US-9475774-B2
Application number	US-201414453220-A
Country	US
Kind code	B2
Filing date	Aug 6, 2014
Priority date	Feb 6, 2012
Publication date	Oct 25, 2016
Grant date	Oct 25, 2016

Abstract

Novel alpha-hydrogen substituted nitroxyl compounds and their corresponding oxidized (oxoammonium cations) and reduced (hydroxylamine) forms, and the use of such compounds, inter alia, for oxidation of primary and secondary alcohols to aldehydes and ketones, respectively; resolution of racemic alcohols; desymmetrization of meso-alcohol; as radicals and spin trapping reagents; and as polymerization agents. Processes for preparing the novel nitroxyl/oxoammonium/hydroxylamine compounds from the corresponding amines, and certain novel amine derivatives and their uses. The compounds and amine precursors are useful as ligands for transition metals and as organocatalysts in e.g., aldol reactions.

First claim

What is claimed is:

1. A compound represented by the structure of formula I:

including enantiomers, disasteromers, optically active, meso and racemic forms thereof, and salts thereof, wherein
Y is

A is an anion;
R 1 is independently at each occurrence (i) phenyl, optionally substituted with one or more substituents selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkoxy and halogen; (ii) naphthyl; or (iii) C 1 -C 6 alkyl;
R 2 is independently at each occurrence a C 1 -C 6 alkyl or a C 3 -C 8 cycloalkyl; and
R 3 is H.

2. The compound according to claim 1 , wherein the compound is represented by the structure of formula I-a:

3. The compound according to claim 1 , wherein the compound is selected from the group consisting of:
a nitroxyl derivative represented by the structure of formula II:

an oxoammonium cation represented by the structure of formula Ill:

a hydroxyamine derivative represented by the structure of formula IV:

4. The compound according to claim 3 , wherein the compound is selected from the group consisting of:
a compound represented by the structure of formula II-a:

a compound represented by the structure of formula III-a:

a compound represented by the structure of formula IVa:

5. The compound according to claim 1 , wherein R 1 is selected from the group consisting of:
phenyl, 4-chiorophenyl, naphthyl, anisyl, mesityl and isopropyl.

6. The compound according to claim 1 , wherein R 2 is selected from the group consisting of methyl and cyclohexyl.

7. The compound according to claim 1 ,
wherein R 1 is the same at each occurrence; or
wherein R 2 is the same at each occurrence; or
wherein R 1 is different at each occurrence; or
wherein R 2 is different at each occurrence; or
wherein R 1 and R 2 are the same; or
wherein R 1 and R 2 are different from each other.

8. The compound according to claim 1 , which is selected from the group consisting of:

and hydroxylamine or oxoammonium derivatives of any of the foregoing.

9. The compound according to claim 1 , which is in a racemic form or in optically active form.

10. An amine derivative represented by the structure of formula V:

wherein
R 1 is independently at each occurrence (i) phenyl, optionally substituted with one or more substituents selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkoxy and halogen; (ii) naphthyl; or (iii) C 1 -C 6 alkyl;

R 2 is independently at each occurrence a C 1 -C 6 alkyl or a C 3 -C 5 cycloalkyl; and
R 3 is H.

11. The amine derivative according to claim 10 , which is selected from the group consisting of:

Assignees

• Technion Res & Dev Foundation

Inventors

• Szpilman Alex M
• Amar Michal

Classifications

• B01J31/0244

  with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine · CPC title

• C07C45/39

  being a secondary hydroxyl group · CPC title

• C07D221/14 Primary

  Aza-phenalenes, e.g. 1,8-naphthalimide · CPC title