New tetraphosphorus ligands have been developed and applied in the rhodium-catalyzed regioselective hydroformylation of a variety of functionalized allyl and vinyl derivatives. Remarkably high linear selectivity was obtained by these tetraphosphorus ligands. The ligand that bears strong electron-withdrawing 2,4-difluorophenyl groups is the most effective one in affording linear aldehydes. The Rh/tetraphosphorus ligand catalyst is highly effective to produce linear aldehydes from functionalized allyl derivatives with heteroatoms or aromatic groups directly adjacent to the allyl group. For vinyl derivatives, the ligand is highly linear selective for acrylic derivatives, styrene, vinyl pyridine, and vinyl phthalimide. Linear to branch ratios of 26:1 and 10:1 were obtained for the hydroformylation of styrene and allyl cyanide, respectively.
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