Green oxidation catalytic system

Patent metadata

Field	Value
Publication number	US-10428043-B2
Application number	US-201515537746-A
Country	US
Kind code	B2
Filing date	Dec 18, 2015
Priority date	Dec 19, 2014
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

Disclosed herein are reaction compositions comprising an oxidation catalyst, a solvent, and a substrate that is dissolved in the solvent. The oxidation catalyst comprises a metal ion complexed with an α-keto acid and a tridentate N,N,O-ligand. Also disclosed herein are methods for oxidizing a C—H bond of a molecule, the methods comprising contacting the molecule with a metal complex comprising a metal ion complexed with a tridentate N,N,O-ligand in the presence of an α-keto acid and a solvent. In some embodiments, the oxidation catalyst or metal complex is linked to a solid support.

First claim

What is claimed is:

1. A reaction mixture comprising
an oxidation catalyst comprising a metal ion complexed with an α-keto acid and a tridentate N,N,O-ligand;
a solvent, wherein the solvent is in contact with the oxidation catalyst; and
a substrate dissolved in the solvent, wherein the solvent and the substrate are different; and wherein the solvent is a polar or polar aprotic solvent.

2. The reaction mixture of claim 1 , wherein the tridentate N,N,O-ligand is of Formula (I):
N(R 11 )(R 12 )—C(R 13 )(R 14 )—(CH 2 ) m —C(R 15 )(R 16 )—N(R 17 )—C(R 18 )(R 19 )—(CH 2 ) n —X  (Formula (I)),

wherein:
R 11 and R 12 are independently H, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 11 and R 12 together with the N they are attached to form an optionally substituted heteroaryl or an optionally substituted heterocyclyl;
R 13 and R 14 are independently H, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 11 and R 13 together with the N and C they are attached to form an optionally substituted heteroaryl or an optionally substituted heterocyclyl, or R 12 and R 14 together form a double bond between the N and C, or R 13 and R 14 together with the C they are attached to form an optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl;
R 15 and R 16 are independently H, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 13 and R 15 together with the carbons they are attached to form an optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 14 and R 16 form a double bond between the carbons they are attached to, or R 15 and R 16 together with the C they are attached to form an optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 11 and R 15 together with the N and C they are attached to form an optionally substituted heterocyclyl or optionally substituted heteroaryl;
R 17 is H, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 15 and R 17 together with the carbon and nitrogen they are attached to form an optionally substituted heteroaryl or an optionally substituted heterocyclyl, or R 16 and R 17 together form a double bond between the N and C, or R 13 and R 17 together with the carbon and nitrogen they are attached to form an optionally substituted heteroaryl or an optionally substituted heterocyclyl;
R 18 and R 19 are independently H, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 17 and R 18 together with the N and C they are attached to form an optionally substituted heteroaryl or an optionally substituted heterocyclyl, or R 17 and R 19 together form a double bond between the N and C, or R 18 and R 19 together with the C they are attached to form an optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 15 and R 18 together with the carbons they are attached to form an optionally substituted heterocyclyl or optionally substituted heteroaryl, or R 13 and R 18 together with the carbons they are attached to form an optionally substituted heterocyclyl or optionally substituted heteroaryl, or R 11 and R 18 together with the carbons they are attached to form an optionally substituted heterocyclyl or optionally substituted heteroaryl;
or one of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 is a solid support linked to Formula (I) with a linker;
X is an oxygen containing moiety;
n is 0, 1, 2, 3, or 4; and
m is 0, 1, 2, 3, or 4.

3. The reaction mixture of claim 2 , wherein X is CO 2 H or CO 2 − .

4. The reaction mixture of claim 1 , wherein the tridentate N,N,O-ligand is N(CH 3 ) 2 CH 2 CH 2 N(CH 3 )CH 2 C(O)O; or

wherein R 21 is a solid support linked to the pyridine ring via a linker, an electron-withdrawing group, an electron donating group, absent, or OR 23 (where R 23 is an electron donating group, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or a solid support linked to O via a linker); and R 22 is H, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl; R 15 and R 16 are independently H, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 15 and R 16 together with the C they are attached to form an optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl; R 18 and R 19 are independently H, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or R 18 and R 19 together with the C they are attached to form an optinally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl; or

wherein R 1 , R 2 , and R 3 are independently H, optionally substituted linear or branched C 1 -C 10 alkyl, optionally substituted linear or branched C 2 -C 10 alkenyl, optionally substituted linear or branched C 2 -C 10 alkynyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl.

5. The reaction mixture of claim, 1 wherein the

Assignees

• Univ Boston

Inventors

• Caradonna John Philip
• Tarves Paul Christopher
• Mcnally Joshua
• Tighe Lauren Gregor

Classifications

• C07C46/04

  of unsubstituted ring carbon atoms in six-membered aromatic rings · CPC title

• C07C2601/16

  the ring being unsaturated · CPC title

• B01J2531/0252

  Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde · CPC title

• C07D211/22

  by oxygen atoms · CPC title

• C07D301/06

  in the liquid phase · CPC title