Transition-metal Catalyzed Synthesis of Carbonyl Compounds Using Formates or Formamides as Carbonyl Sources

Abstract

Various available approaches for catalytic carbonylation reactions using formates and formamides with transition metal catalysts are reviewed. Pd complexes catalyze the hydroesterification or hydrocarbamoylation of alkynes using aryl formates or formamides, respectively, as the carbonyl sources. The esterification of aryl halides with aryl formates proceeds in the presence of a Pd catalyst with suitable ligands. Using a Cu complex with a bulky bidentate phosphine ligand is used as a catalyst, boraformylation and silaformylation of allenes efficiently proceeds using alkyl formates as a formyl source.

Progress on transition metal catalyzed asymmetric hydroesterification, hydrocarboxylation, and hydroamidation reactions of olefins

“…Efforts have also been made to use CO surrogates for hydroesterification reactions. 56 Shi and coworkers reported a Pd-catalyzed asymmetric hydroesterification process for alkenylphenols ( 114 ) with phenyl formate using ( R )-(−)-DTBM-SEGPHOS ( L38 ) as a ligand (Scheme 56). 57,58 A variety of optically active dihydrocoumarins ( 115 ) were obtained in generally good yields with up to 91% ee.…”