Introducing the Catalytic Amination of Silanes via Nitrene Insertion Article Swipe

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Chemistry Nitrene Silanes Homolysis Alkyne Amination Alkene Photochemistry Bond cleavage Migratory insertion Density functional theory Catalysis Stereochemistry Polymer chemistry Combinatorial chemistry Computational chemistry Organic chemistry Radical Silane

Anabel M. Rodríguez , Jorge Pérez‐Ruíz , Francisco Molina , Ana Poveda , Raúl Pérez‐Soto , Feliu Maseras , M. Mar Díaz‐Requejo , Pedro J. Pérez ·

YOU? · · 2022 · Open Access · · DOI: https://doi.org/10.1021/jacs.2c03739 · OA: W4281693652

The direct functionalization of Si-H bonds by the nitrene insertion methodology is described. A copper(I) complex bearing a trispyrazolylborate ligand catalyzes the transfer of a nitrene group from PhI═NTs to the Si-H bond of silanes, disilanes, and siloxanes, leading to the exclusive formation of Si-NH moieties in the first example of this transformation. The process tolerates other functionalities in the substrate such as several C-H bonds and alkyne and alkene moieties directly bonded to the silicon center. Density functional theory (DFT) calculations provide a mechanistic interpretation consisting of a Si-H homolytic cleavage and subsequent rebound to the Si-centered radical.