1.
Angew Chem Int Ed Engl
; 58(15): 5119-5123, 2019 Apr 01.
Artículo
en Inglés
| MEDLINE
| ID: mdl-30694004
RESUMEN
A new concept for selectivity control in carbocation-driven reactions has been identified which allows for the chemo-, regio-, and stereoselective addition of nucleophiles to alkynes-assisted vinyl cation formation-enabled by a Li+ -based supramolecular framework. Mechanistic analysis of a model complex (Li2 NTf2 + â 3 H2 O) confirms that solely the formation of a complex between the incoming nucleophile and the transition state of the alkyne protonation is responsible for the resulting selective Nâ addition to the vinyl cation. Into the bargain, a general, operationally simple synthetic procedure to previously inaccessible vinyl triflimides is provided.