Easily accessible BINOL-based monodentate phosphite ligand L1 and hybrid ligand L2 have been synthesized in good yield by following a one-pot, two-step protocol. A single 31P resonance at 146.6 ppm confirmed the formation of L1. Subsequent 1-2D NMR and mass spectrometric analysis authenticated the existence of L1. These ligands afforded excellent activity and regio-selectivity in the Rh-catalyzed AHF of styrenic substrates. L1 showed excellent regioselectivity but did not discriminate between the two enantiomers, while L2 displayed an enantiomeric excess (ee) of up to 20%. In our attempts to understand the reasons for low ee, the coordination behavior of L2 was investigated. The coordination study revealed that L2 coordinates with the Rh as a monodentate ligand, although there are two P-sites. It was found that only the phosphine arm was coordinated to the Rh and the phosphite arm stayed away from the Rh core at the ambient temperature, leading to moderate ee.Graphical abstractOne-step synthesis of a phosphite (L1) and a phosphine-phosphite (L2) ligand and their implication in the asymmetric hydroformylation of olefins with excellent regioselectivity (>95%) and moderate enantioselectivity (up to 20%) is reported.

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