Valuable polyester monomers and plasticizers-1,4-cyclohexanedimethanol (CHDM), 1,4-cyclohexanedicarboxylic acid (CHDA), and 1,2-cyclohexanedicarboxylates-have been prepared by a new strategy. The synthetic processes involve a proline-catalyzed formal [3+1+2] cycloaddition of formaldehyde,