Enantioselective transformation of α,β-unsaturated aldehydes using chiral organic catalysts

A process for catalyzing a reaction between an α,β-unsaturated aldehyde and a second reactant by lowering the energy level of the lowest unoccupied molecular orbital (LUMO) of the aldehyde, comprising:

• contacting an α,β-unsaturated aldehyde with the second reactant in the presence of a catalyst comprised of an acid addition salt of compound (IIA) or (IIB) and a Bronsted acid
• wherein:
• R1 is selected from the group consisting of C1-C12 hydrocarbyl, substituted C1-C12 hydrocarbyl, heteroatom-containing C1-C12 hydrocarbyl, and substituted heteroatom-containing C1-C12 hydrocarbyl;
• R2 has the structure —(L)m—CR6R7R8 wherein m is zero or 1, L is C1-C6 alkylene, and R6, R7 and R8 are C1-C12 hydrocarbyl;
• R3 and R4 are independently selected from the group consisting of hydrogen, halo, hydroxyl, C1-C12 hydrocarbyl, substituted C1-C12 hydrocarbyl, heteroatom-containing C1-C12 hydrocarbyl, and substituted heteroatom-containing C1-C12 hydrocarbyl;
• and
• R5 is a cyclic group optionally substituted with 1 to 4 non-hydrogen substituents and containing zero to 3 heteroatoms,
• wherein the second reactant is capable of reacting with the aldehyde by virtue of the lowered LUMO of the aldehyde in the presence of the catalyst.