Electrophilic activation of water by a carbene catalyzed by a copper surface

Abstract

Carbenes are among the most versatile organic intermediates, capable of exhibiting radical, electrophilic, or nucleophilic reactivity. Harnessing this versatility for synthesis requires precise control over carbene philicity. In reactions with protic molecules such as water or alcohols, free carbenes are generally nucleophilic and react exclusively via proton transfer to form carbenium ions. Here we demonstrate a fundamentally different reactivity mode: electrophilic activation of water by an archetypal aryl carbene catalyzed by a copper surface. Surface infrared spectroscopy, bond-resolved scanning tunneling microscopy, and theoretical modeling reveal that the carbene reacts with the water as an electrophile, forming a surface-stabilized ylide that is subsequently deprotonated. This heterogeneous pathway contrasts sharply with the behavior of metal-free carbenes in solution and cryogenic matrices, where reaction proceeds exclusively through proton transfer from the water to the carbene. These results provide molecular-level insight into surface-catalyzed modulation of carbene reactivity and establish heterogeneous catalysis as a platform for accessing otherwise inaccessible carbene–water reaction pathways.