In this study, a series of γ,γ-disubstituted and β,γ-disubstituted allylic alcohols were prepared and successfully hydrogenated using suitable N,P-based Ir complexes. High yields and excellent enantioselectivities were obtained for most of the substrates studied. This investigation also revealed the effect of the acidity of the N,P−Ir-complexes on the acidsensitive allylic alcohols. DFT ΔpK a calculations were used to explain the effect of the N,P-ligand on the acidity of the corresponding Ir-complex. The selectivity model of the reaction was used to accurately predict the absolute configuration of the hydrogenated alcohols.
A highly efficient regio-and enantioselective 8 monohydrogenation of 1,4-dienes has been realized using an 9 iridium catalyst with a chiral N,P-ligand under mild conditions.
10The substrate scope was studied and included both unfunction-11 alized as well as functionalized substituents on the meta-or para-
A novel OXONE ® mediated direct difunctionalization of alkenes with NaNO 2 in aqueous acetonitrile for the synthesis of a-nitrooximes was developed. The a-nitrooximes were readily prepared in moderate to high yields at room temperature under mild reaction conditions. The present protocol offers an easy and environmentally benign approach to access various a-nitrooximes derived from styrene derivatives.
A highly efficient method for direct nitration-oximization of styrene derivatives using tert-butyl nitrite (t-BuONO) in DMSO was developed. The present method offers a convenient and practical approach for the synthesis of α-nitrooximes in moderate to high yields. The salient features entail mild reaction conditions, metal-free reagent, environmentally benign solvent and simple experimental procedure.
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