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The use of molecular oxygen as the terminal oxidant in transition metal catalyzed oxidative process is an appealing and challenging task in organic synthetic chemistry. Here, we report a Ni‐catalyzed hydroxylarylation of unactivated alkenes enabled by a β‐diketone ligand with high efficiency and excellent regioselectivity employing molecular oxygen as the oxidant and hydroxyl source. This reaction features mild conditions, broad substrate scope and incredible heterocycle compatibility, providing a variety of β‐hydroxylamides, γ‐hydroxylamides, β‐aminoalcohols, γ‐aminoalcohols, and 1,3‐diols in high yields. The synthetic value of this methodology was demonstrated by the efficient synthesis of two bioactive compounds, (±)‐3′‐methoxyl citreochlorol and tea catechin metabolites M4. [ABSTRACT FROM AUTHOR]

A facile method for the construction of the aspidosperma core from indoles functionalized with a nonterminal N‐allenamide and dimethyl methylenemalonate is described. Various polysubstituted tetracyclic spiroindolines (27 examples) were afforded in good yields (61–90 %) with >99/1 dr and >99/1 Z/E selectivity under mild conditions. The annulation reaction provides straightforward access to the tetracyclic spiroindoline skeleton with substituents at the C5 position occurring in many natural products. As an application of this reaction, the total synthesis of three important natural products, (−)‐deoxoapodine, (−)‐kopsifoline D and (±)‐melotenine A, was possible in short routes from tryptamine. [ABSTRACT FROM AUTHOR]