Alpha-Hydrogen Substituted Nitroxyls And Derivatives Thereof As Catalysts
AssigneeTechnion Research & Development Foundation Limited
InventorsAlex M. Szpilman, Michal Amar
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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.
Claims23
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;
- R1 and R2 are each independently at each occurrence an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, or an unsubstituted or substituted aryl;
- and
- R3 is independently at each occurrence H, halo, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, heterocyclyl, heteroaryl, hydroxy, alkoxy, aryloxy, cycloalkyloxy, heterocyclyloxy, heteroaryloxy, formyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, cycloalkylamino, heterocyclylamino, heteroarylamino, amido, alkylamido, dialkylamido, arylamido, diarylamido, alkylarylamido, cycloalkylamido, heterocyclylamido, heteroarylamido, cyano, nitro, carboxyl, carboxyalkyl, carboxyaryl, acyl, —S(═O)Ra, —S(═O)2Ra—C(═O)Ra or —C(═O)ORa, wherein Ra is independently at each occurrence alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, heterocyclyl or heteroaryl;
- wherein each of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, heterocyclyl or heteroaryl may be unsubstituted or substituted.
An amine derivative represented by the structure of formula V or formula V-a:
- wherein
- R1 and R2 are each independently at each occurrence an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, or an unsubstituted or substituted aryl;
- and
- R3 is independently at each occurrence H, halo, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, heterocyclyl, heteroaryl, hydroxy, alkoxy, aryloxy, cycloalkyloxy, heterocyclyloxy, heteroaryloxy, formyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, cycloalkylamino, heterocyclylamino, heteroarylamino, amido, alkylamido, dialkylamido, arylamido, diarylamido, alkylarylamido, cycloalkylamido, heterocyclylamido, heteroarylamido, cyano, nitro, carboxyl, carboxyalkyl, carboxyaryl, acyl, —S(═O)Ra, —S(═O)2Ra—C(═O)Ra or —C(═O)ORa, wherein Ra is independently at each occurrence alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, heterocyclyl or heteroaryl;
- wherein each of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, heterocyclyl or heteroaryl may be unsubstituted or substituted;
- wherein
- R1 is an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, or an unsubstituted or substituted aryl;
- R2 and R4 are each H, an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, or an unsubstituted or substituted aryl;
- and
- R3 is independently at each occurrence H, halo, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, heterocyclyl, heteroaryl, hydroxy, alkoxy, aryloxy, cycloalkyloxy, heterocyclyloxy, heteroaryloxy, formyl, —S(═O)Ra, —S(═O)2Ra—C(═O)Ra, —C(═O)ORa, wherein Ra is independently at each occurrence alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, heterocyclyl or heteroaryl;
- amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, cycloalkylamino, heterocyclylamino, heteroarylamino, amido, alkylamido, dialkylamido, arylamido, diarylamido, alkylarylamido, cycloalkylamido, heterocyclylamido, heteroarylamido, cyano, nitro, carboxyl, carboxyalkyl, carboxyaryl, acyl, wherein each of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, heterocyclyl or heteroaryl may be unsubstituted or substituted.
Dependencies are inferred from the claim text.