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

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 is an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkoxy group, or an aryloxy group;
• wherein R2 is O—R6 or —N—(R6)2;
• 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 is 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:
• wherein each R6, 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, R3 is methyl, R4 is H, each R5 is phenyl, and M is Ru, then Y is P.