Ligand relay catalysis for cobalt-catalyzed sequential hydrosilylation and hydrohydrazidation of terminal alkynes

In organic chemistry, performing sequential catalytic cycles with a single catalyst improves efficiency. Here the authors present a methodology to functionalize alkynes with nitrogen and silicon atoms, through two catalytic cycles with a homogeneous cobalt catalyst, which is bound to different ligands in each cycle. Sequential double hydrofunctionalizationalization of alkynes is a powerful method to construct useful vicinal compounds. Herein, we report a cobalt-catalyzed sequential hydrosilylation/hydrohydrazidation of alkynes to afford 1,2-N,Si compounds via ligand relay catalysis. A phenomenon of ligand relay is found that the tridentate anionic N-ligand (OPAQ) could capture the cobalt ion from bidentate neutral P-ligand (Xantphos) cobalt complex. This protocol uses three abundant chemical feedstocks, alkynes, silanes, and diazo compounds, and also features operationally simple, mild conditions, low catalyst loading (1 mol%), and excellent functional group tolerance. The 1,2-N,Si compounds can be easily further derivatized to afford various substituted silane derivatives via Si-H functionalization, alcohols via Fleming-Tamao oxidation, free amines and amides via N-N bond cleavage and protection. The asymmetric reaction could also be carried out to afford chiral products with up to 86% ee. The ligand relay has been supported by control experiments and absorption spectra.

Automated summary

In this study, a method for sequentially catalyzing alkynes with nitrogen and silicon atoms using a cobalt catalyst is presented. The method involves two catalytic cycles with different ligands, and demonstrates high efficiency, simple operation, and excellent functional group tolerance. The study also reveals a phenomenon of ligand relay, where certain ligands can capture metal ions from other ligands.