Method for oxidative cleavage of compounds with unsaturated double bond

Patent metadata

Field	Value
Publication number	US-11407692-B2
Application number	US-202016860690-A
Country	US
Kind code	B2
Filing date	Apr 28, 2020
Priority date	Jan 2, 2020
Publication date	Aug 9, 2022
Grant date	Aug 9, 2022

Abstract

A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method includes the steps of:
(A) providing a compound (I) with an unsaturated double bond, a trifluoromethyl-containing reagent, and a catalyst;

wherein, the catalyst is represented by Formula (II):

M(O) m L 1 y L 2 z   (II);

wherein, M, L 1 , L 2 , m, y, z, R 1 , R 2 and R 3 are defined in the specification; and
(B) mixing the compound with an unsaturated double bond and the trifluoromethyl-containing reagent to perform an oxidative cleavage of the compound with the unsaturated double bond by using the catalyst in air or under oxygen atmosphere condition to obtain a compound represented by Formula (III):

First claim

What is claimed is:

1. A method for oxidative cleavage of a compound with an unsaturated double bond, comprising the steps of:
(A) providing a compound (I) with an unsaturated double bond, a trifluoromethyl-containing reagent, and a catalyst;

wherein, R 1 and R 2 are each independently H, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-18 aryl, or C 4-18 heteroaryl, or R 1 and R 2 are fused to be C 6-18 aralkyl; R 3 is H, C 1-10 alkyl, C 3-10 cycloalkyl, C 6-10 aryl, or C 4-10 heteroaryl, with the proviso that R 1 , R 2 and R 3 are not H at the same time;
wherein the catalyst is represented by Formula (II):
M(O) m L 1 y L 2 z   (II)

wherein, M is a metal selected from the group consisting of IVB, VB, VIB, and actinides;
L 1 and L 2 are each a ligand;
m and y are integers greater than or equal to 1; and
z is an integer greater than or equal to 0;
(B) mixing the compound with the unsaturated double bond and the trifluoromethyl-containing reagent to perform an oxidative cleavage of the compound with the unsaturated double bond by using the catalyst in air or under oxygen atmosphere condition to obtain a compound represented by Formula (III):

2. The method of claim 1 , wherein R 1 and R 2 are each independently H, C 1-10 alkyl, C 3-10 cycloalkyl, C 6-14 aryl, or C 4-10 heteroaryl, or R 1 and R 2 are fused to be C 6-12 aralkyl; R 3 is H, C 1-6 alkyl, C 3-6 cycloalkyl, C 6-10 aryl, or C 4-10 heteroaryl.

3. The method of claim 1 , wherein L 1 is selected from the group consisting of OTf, OTs, NTf 2 , halogen, RC(O)CH 2 C(O)R, OAc, OC(O)R, OC(O)CF 3 , OMe, OEt, O-iPr, and butyl, wherein R is alkyl.

4. The method of claim 1 , wherein L 2 is selected from the group consisting of Cl, H 2 O, CH 3 OH, EtOH, THF, CH 3 CN,

and ligand containing C═N unit.

5. The method of claim 4 , wherein the ligand containing C═N unit comprises pyridine, oxazole, oxazoline, or imidazole.

6. The method of claim 5 , wherein the ligand containing C═N unit is represented by Formula (V):

wherein R 6 and R 7 are each independently H, C 1-5 alkyl or C 3-6 cycloalkyl.

7. The method of claim 4 , wherein the ligand containing C═N unit is represented by Formula (IV):

wherein, R 4 and R 5 are each independently halogen, nitro, C 1-10 alkyl, C 6-18 aryl, or C 4-18 heteroaryl.

8. The method of claim 1 , wherein the catalyst represented by Formula (II) is MoO 2 Cl 2 , V(O)Cl 3 , V(O)(O-iPr) 3 , V(O)Cl 2 , V(O)(OAc) 2 , V(O)(O 2 CCF 3 ) 2 , Ti(O)(acac) 2 , Zr(O)Cl 2 , Hf(O)Cl 2 , Nb(O)Cl 2 , MoO 2 (acac) 2 , V(O)(OTs) 2 , VO(OTf) 2 , or V(O)(NTf 2 ) 2 .

9. The method of claim 1 , wherein the catalyst represented by Formula (II) is any one of formulas (II-1) to (II-4):

10. The method of claim 1 , wherein the trifluoromethyl-containing reagent is 3,3-Dimethyl-1-(trifluoromethyl)-1,2-benziodoxole, 3,3-Dimethyl-1-(perfluroalkyl)-1,2-benziodoxole, 3-oxo-1-(trifluoromethyl)-1,2-benziodoxole, 3-oxo-1-(perfluroalkyl)-1,2-benziodoxole), trifluomethyl dibenzothiophenium salts, perfluoroalkyl dibenzothiophenium salts, CF 3 SO 2 Na, or CF 3 (CF 2 ) n SO 2 Na, wherein n is an integer of 1 to 6.

11. The method of claim 1 , wherein step (B) further obtains a trifluoroketone- or trifluoroaldehyde-containing compound represented by the following formula (VI), trifluoroalkyl alcohol represented by the following formula (VII) or a combination thereof:

wherein R 3 is H, C 1-10 alkyl, C 3-10 cycloalkyl, C 6-10 aryl, or C 4-10 heteroaryl; n is an integer of 0 or 1 to 6.

Assignees

• Univ Nat Tsing Hua

Inventors

• Chen Chien-Tien
• Liao Yi-Ya
• Chen ya-pei

Classifications

• B01J31/2243

  At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand · CPC title

• C07D413/06 Primary

  linked by a carbon chain containing only aliphatic carbon atoms · CPC title

• C07C227/02

  Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols · CPC title

• B01J31/1835

  comprising aliphatic or saturated rings · CPC title

• B01J31/2256

  being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional ligands · CPC title