Green oxidation catalytic system

Patent metadata

Field	Value
Publication number	US-2018297976-A1
Application number	US-201515537746-A
Country	US
Kind code	A1
Filing date	Dec 18, 2015
Priority date	Dec 19, 2014
Publication date	Oct 18, 2018
Grant date	—

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.

2 . (canceled)

3 . 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.

4 . (canceled)

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

6 . 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 optionally 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.

7 . (canceled)

Assignees

• Univ Boston

Inventors

• Caradonna John Philip
• Tarves Paul C
• Mcnally Joshua
• Gregor Lauren

Classifications

• C07C45/27

  by oxidation (with ozone C07C45/40) · CPC title

• B01J2531/842

  Iron · CPC title

• B01J31/18

  containing nitrogen, phosphorus, arsenic or antimony {as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms (double metal cyanides B01J27/26; N-heterocyclic carbenes B01J31/2265)} · CPC title

• C07C45/33

  of CHx-moieties · CPC title

• C07C29/50

  with molecular oxygen only · CPC title