Development of highly efficient platinum catalysts for hydroalkoxylation and hydroamination of unactivated alkenes

Abstract Hydrofunctionalization, the direct addition of an X–H (e.g., X=O, N) bond across alkene, is a desirable strategy to make heterocycles that are important structural components naturally occurring molecules. Described here design and discovery “donor–acceptor”-type platinum catalysts highly effective in both hydroalkoxylation hydroamination unactivated alkenes over broad range substrates under mild conditions. A number alkene substitution patterns accommodated, including tri-substituted, 1,1-disubstituted, ( E )-disubstituted, Z )-disubstituted even mono-substituted double bonds. Detailed mechanistic investigations suggest plausible pathway includes unexpected dissociation/re-association electron-deficient ligand form alkene-bound intermediate. These studies help understand origins high reactivity exhibited by catalytic system, provide foundation for rational chiral towards asymmetric hydrofunctionalization reactions.