Synthesis of fluoro hemiacetals via transition metal-catalyzed fluoro ester and carboxamide hydrogenation

Patent metadata

Field	Value
Publication number	US-11370736-B2
Application number	US-202016837698-A
Country	US
Kind code	B2
Filing date	Apr 1, 2020
Priority date	Apr 1, 2019
Publication date	Jun 28, 2022
Grant date	Jun 28, 2022

Abstract

This application is directed to use of transition metal-ligand complexes to hydrogenate fluorinated esters and carboxamides into fluorinated hemiacetals. Methods for synthesis of certain ligands are also provided.

First claim

What is claimed is:

1. A process for producing a fluorinated hemiacetal, said process comprising:
reacting a fluorinated precursor with hydrogen gas in the presence of a transition metal-ligand complex and a base,
wherein said fluorinated precursor is of the general formula (I):

wherein R 1 is an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkoxy group, or an aryloxy group;
wherein R 2 is O—R 6 or —N—(R 6 ) 2 ;
wherein at least one of R 1 and R 2 is fluorinated or perfluorinated;
wherein said transition metal-ligand complex is of general formula (II), general formula (III), general formula (IV), or general formula (V):

wherein R 3 is C 1-6 alkyl, C 3-6 cycloalkyl, aryl, heteroaryl, or arylalkyl;
wherein R 4 is H, C 1-6 alkyl, C 3-6 cycloalkyl, aryl, heteroaryl, or arylalkyl;
wherein each R 5 , independently, is an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkoxy group, or an aryloxy group;
wherein Y is —P or —P═O;
wherein M is a transition metal;
wherein m is 1, 2, 3, 4, or 5;
wherein n is 1, 2, 3, 4, or 5;
wherein q is 0, 1, or 2;
wherein each of X 1 and X 2 , independently, is a ligand with a formal charge of −1 or 0;
wherein X 3 is absent or is a ligand with a formal charge of −1 or 0;
wherein each alkyl, cycloalkyl, aryl, heteroaryl, arylalkyl, alkoxy, aryloxy, or aromatic group may be substituted or unsubstituted; and
wherein said fluorinated hemiacetal is of the general formula:

wherein each R 6 , independently, is H, F, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, or an arylalkyl group; and
wherein if the transition metal-ligand complex is of general formula (II), m is 1, n is 1, q is 0, R 3 is methyl, R 4 is H, each R 5 is phenyl, and M is Ru, then Y is P.

2. The process of claim 1 , wherein said transition metal-ligand complex is of general formula (IIa), general formula (IIIa), general formula (IVa), general formula (Va), general formula (IIb), general formula (IIIb), general formula (IVb), or general formula (Vb):

3. The process of claim 1 , wherein R 1 is C 1-6 fluoroalkyl, C 3-6 fluorocycloalkyl, fluoroaryl, fluoroheteroaryl, fluoroarylalkyl, fluoroalkoxy, or fluoroaryloxy.

4. The process of claim 1 , wherein R 6 is C 1-6 fluoroalkyl, C 3-6 fluorocycloalkyl, fluoroaryl, fluoroheteroaryl, or fluoroarylalkyl.

5. The process of claim 1 , wherein each R 6 is, independently, selected from the group consisting of H, F, CF 3 , CHF 2 , CH 2 F, CH 2 CF 3 , CH 2 CHF 2 , CH 2 CH 2 F, CF 2 CH 3 , CF(CH 3 ) 2 , CF 2 CH(OH)C 2 H 5 , CHFCH 2 C(═CH 2 )CH 3 , CF 2 CH═CHCH 3 , CF 2 CH 2 CH═CHCH 3 , CH 2 (CH 2 ) 2 CH═CHCH 3 , CF 2 C 6 H 5 ,

and

6. The process of claim 1 , wherein each of X 1 , X 2 , and X 3 is independently alkyl, aryl, alkoxy, aryloxy, carboxylate, halo, hydrido, hydrogen, hydroxyl, NO, OTf (triflate), OTs (tosylate), phosphate, BH 4 , a nitrile, an amine, carbonyl, an ether, a phosphine, a phosphine oxide, a phosphite, or a sulfoxide.

7. The process of claim 1 , wherein each R 5 , independently, is an aryl group or an arylalkyl group.

8. The process of claim 1 , wherein M is Ru or Ir.

9. The process of claim 8 , wherein the transition metal-ligand complex comprises one of the following structures:

10. The process of claim 1 , wherein the fluorinated precursor is a fluorinated ester.

Assignees

• Triad Nat Security Llc

Inventors

• Dub Pavel A
• Batrice Rami J
• Gordon John C

Classifications

• C07C41/50 Primary

  by reactions producing [IMAGE cpc-sch-C07C-0958.gif] groups · CPC title

• C07F15/0053

  without a metal-carbon linkage · CPC title

• C07C41/20 Primary

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title

• C07C29/145

  with hydrogen or hydrogen-containing gases · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title