Palladium precatalyst embodiments for enantioselective chemical reactions and methods of making and using the same

A chiral precatalyst having a structure according to Formula I

• wherein:
• the Pd atom has an oxidation state of 0;
• the A group is a compound comprising at least one olefin moiety capable of coordinating with Pd(0), provided that the A group is not (1 E,4E)-1,5-diphenylpenta-1,4-dien-3-one or methyl (E)-2-acetoxy-3,5-diphenylpent-4-enoate;
• each of X1 and X2 independently are selected from phosphorus or nitrogen, provided that if one of X1 or X2 is nitrogen, then the other of X1 or X2 is phosphorus and is not nitrogen;
• each of R5 and R6 independently is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group;
• R7 is an aromatic group, an aliphatic group, a haloaliphatic group, a haloheteroaliphatic group, or a heteroaliphatic group;
• the linker, if present, comprises a chiral heteroaliphatic group having a formula
• wherein Z comprises an aliphatic group, an aromatic group, or an organic functional group, wherein the aliphatic, aromatic, or organic functional group comprises a chiral substituent and/or an asymmetric center;
• and each of W1, W2, Y1, and Y2 independently are selected from oxygen, sulfur, or NR wherein R is hydrogen, aliphatic, or aromatic;
• each of R9 and R10, if present, independently is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group;
• each n is 1 or each n is 0;
• m is 1 or 0;
• and
• (i) if each n is 1, then R8 is an aromatic group, an aliphatic group, a haloaliphatic group, a haloheteroaliphatic group, or a heteroaliphatic group and is bound to X2 via a single bond and no ring B is formed;
• or
• (ii) if each n is 0, then R8 is a carbon atom that forms the ring B with X2 and is bound to X2 via a double bond, wherein the ring B is an aromatic or heterocyclic ring comprising a chiral substituent or an asymmetric center;
• and
• provided that for Formula I, the compound is not or is other than