α-Aminocarbene-Mediated Si–H Insertion: Deoxygenative Silylation of Aromatic Amides with Silanes

Abstract

While metal carbene-mediated Si−H insertion reactions have become a powerful strategy to build new C−Si bonds, the utilization of α-aminocarbene intermediates generated from readily available precursors in the Si−H insertion reaction remains a longstanding challenge. Herein, we develop a practical and general strategy to synthesize α-aminosilanes through a deoxygenative cross-coupling of amides and silanes mediated by Sm/SmI 2 . Given the simplicity and versatility, this methodology represents a fascinating example for the effective utilization of inert amides as α-aminocarbene precursors in organic synthesis.

beta-Silicon Effect Enables Metal-Free Site-Selective Intermolecular Allylic C−H Amination

“…37,38 However, current strategies rely heavily on functional group manipulations. [41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56] Methods via direct C-H functionalization are scarce and still suffer from the use of stoichiometric amounts of strong bases, limited substrate scope, poor regioselectivities, and/or harsh reaction conditions. [57][58][59][60][61][62] Herein, we report a mild and selective seleniumcatalyzed allylic C-H amination reaction of allyl silanes towards the diverse synthesis of allyl α-amino silanes (Scheme 1d).…”

Copper-Catalyzed General and Selective α-C(sp3)–H Silylation of Amides via 1,5-Hydrogen Atom Transfer

“…In light of this, the preparation of α-aminosilanes has garnered increasing attention in the past few decades, − and some significant strategies involving silylation of imines, hydroamination of vinylsilanes, hydrosilylation of enamides, decarboxylative silylation of amino acids, deoxygenative silylation of amides, and other pathways have been developed. However, these methods typically rely on the utilization of harsh reaction conditions, prefunctionalized substrates, or multistep transformations.…”

Copper/Chiral Phosphoric-Acid-Catalyzed Intramolecular Reductive Isocyanide-Alkene (1 + 2) Cycloaddition: Enantioselective Construction of 2-Azabicyclo[3.1.0]hexanes

“…To circumvent these limitations, a proper alkenyl N–H free α-aminocarbenoid precursor is proposed (Scheme b). α-Aminocarbenoids are generally produced by Sm­(Mg)/SmI 2 -mediated deoxygenation of amides, and their synthetic application includes homodimerization, C–H insertion, Si–H insertion, cyclopropanation, etc. − To the best of our knowledge, the asymmetric transformation of α-aminocarbenoids is unprecedented.…”