Concatenating Structural Constraint Effects at Tin for the Sequential Generation, Stabilization, and Transfer of Acyclic Aminocarbenes

Structural constraint approaches have been employed toward different ends in recent years, from augmenting the nucleophilicity in pyramidalized low-valent p-block compounds to enhancing the Lewis acidities at planarized tetravalent p-block elements. While previous studies exploited these effects separately, this work introduces a strategy to concatenate structural constraint approaches at individual stages of a reaction sequence in a row to unlock a synthetic path unattainable by conventional methodologies. The boosted nucleophilicity resulting from the constrained tetracoordinated calix4pyrrolato stannate(II) dianion enables the reductive formation of sterically unprotected acyclic aminocarbenes. These amino carbenes are stabilized at the concomitantly formed square-planar stannane(IV) as air-stable adducts. Transfer of the carbenes onto copper(I) by cooperativity of the calix4pyrrole ligand finalizes this protocol to hitherto unreported yet prototypical carbene complexes. Detailed spectroscopic and quantum theoretical analyses establish the synergy of structural constraints and element–ligand cooperation as the linchpin to this reaction path and its selectivity.