Asymmetric 1,4-reductions of and 1,4-additions to enoates and related systems

The method represented by the generalized reaction depicted in Scheme 1:

• wherein
• Z represents an electron withdrawing group selected from the group consisting of formyl, acyl, —CN, —C(O)OR, —C(O)N(R)2, nitro, nitroso, —S(O)2R, —S(O)2N(R)2, —C(NR)—R, —C(NOR)—R, and —C(NN(R)2)—R;
• R represents independently for each occurrence hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or —(CH2)m—R80;
• R1, R2, and R3 are independently selected from the group consisting of H, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, —Si(R)3, and —(CH2)m—R80;
• the transition metal catalyst consists essentially of an asymmetric bidentate ligand and a copper complex selected from the group consisting of copper carboxylates, copper carbonates, copper sulfates, copper sulfonates, copper halides, copper trifluoroborates, copper phosphates and mixtures thereof;
• Nu represents hydrogen;
• NuW is a silane or polymethylhydrosiloxane (PMHS);
• the base is selected from the group consisting of alkoxides, phenoxides, and amides;
• taken together, any two groups selected from Z, R1, R2, and R3 may form a ring comprising a total of 5-7 atoms in the backbone of said ring;
• said ring may comprise one or two heteroatoms in its backbone;
• and said ring may bear instances of R;
• R80 represents independently for each occurrence amyl, cycloalkyl, cycloalkenyl heterocyclyl, or polycyclyl;
• m is an integer in the range 0 to 8 inclusive;
• and
• the carbon marked with an asterisk in compound 2 is asymmetric.