Synthesis of fluoro hemiacetals via transition metal-catalyzed fluoro ester and carboxamide hydrogenation
AssigneeTriad National Security, LLC
InventorsPavel A. Dub, Rami J. Batrice, John C. Gordon
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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.
Claims59
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 R1 comprises an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkoxy group, or an aryloxy group;
- wherein R2 comprises —O—R6 or —N—(R6)2;
- wherein each R6, independently, is H, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, or an arylalkyl group;
- wherein at least one of R1 and R2 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 R3 comprises C1-6 alkyl, C3-6 cycloalkyl, aryl, heteroaryl, or arylalkyl;
- wherein R4 is H, C1-6 alkyl, C3-6 cycloalkyl, aryl, heteroaryl, or arylalkyl;
- wherein each R5, 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 X1 and X2, independently, is a ligand with a formal charge of −1 or 0;
- wherein X3 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 (VI):
A method for preparing a transition metal-SNP ligand complex, said method comprising reacting a transition metal complex with an SNP ligand, thereby forming the transition metal-SNP ligand complex.
A method for preparing an SNPO, SONPO, or SO2NPO ligand, said method comprising reacting an allyl phosphine oxide with an amino alkyl sulfide, amino alkyl sulfoxide, or amino alkyl sulfonyl,
- wherein said allyl phosphine oxide is of general formula (VII):
- wherein each R5, 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 x is 0, 1, 2, 3, or 4;
- wherein said amino alkyl sulfide, amino alkyl sulfoxide, or amino alkyl sulfonyl is of general formula (VIII):
- wherein R3 is C1-6 alkyl, C3-6 cycloalkyl, aryl, heteroaryl, or arylalkyl;
- wherein y is 2, 3, 4, 5, or 6;
- wherein q is 0, 1, or 2;
- wherein each alkyl, cycloalkyl, aryl, heteroaryl, arylalkyl, or aromatic group may be substituted or unsubstituted;
- and wherein said SNPO, SONPO, or SO2NPO ligand is of general formula (IX):
- wherein n is 1, 2, 3, 4, or 5, and
- wherein m is 1, 2, 3, 4, or 5.
Dependencies are inferred from the claim text.