This Perspective article provides an overview of the recent advancements in the field of intra- and inter-molecular C-N, C-O and C-P bond formation by hydroamination, hydroalkoxylation, hydrophosphination, hydrophosphonylation or hydrophosphinylation of unactivated alkenes, including allenes, 1,3-dienes and strained alkenes, promoted by (chiral) homogeneous catalysts based on earth abundant elements of the s and p blocks, the first row transition metals and the rare-earth metals. The relevant literature from 2009 until late 2014 has been covered.
With the rising interest in asymmetric catalysis promoted by earth‐abundant elements, a chiral ligand will undoubtedly be the most valuable unit of the catalyst. The first proof of concept of the use of a multitask chiral ligand in an asymmetric assisted tandem catalysis protocol that successively combines metallo‐ and organocatalytic processes is reported herein. In this protocol, the chiral ligand of the newly designed rare‐earth catalyst of the first reaction is converted into a novel chiral organocatalyst for the second transformation by the simple addition of HCl. The observation of some enantioinduction in the tandem sequence—alkyne hydroamination followed by enantioselective Friedel–Crafts alkylation—confirms the relay of the chiral N,N,N′,N′‐tetradentate ligand and the importance of its pyridylmethylamine scaffold.
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