Blueprints for the Geometric Control of N-Heterocyclic Carbene–Carbodiimide Isomers

Abstract

Rational control of the 3D presentation of atoms—stereochemistry—lies at the heart of synthetic organic and materials chemistries. Here, researchers report detailed computational studies on conformational isomerism in N-heterocyclic carbene–carbodiimide (NHC–CDI) zwitterionic adducts. By varying the steric and electronic parameters of the NHC and CDI components, criteria for controlling isomerization thermodynamics and predicting energetically favorable conformations are identified. These criteria is validated experimentally using a novel synthetic approach to NHC–CDIs, which exploits the thermodynamic equilibrium between sterically unencumbered NHC dimers to access NHC–CDI adducts with low barriers to conformational isomerization, including the first example of an (E/E)-NHC–CDI.

Publication
ChemistryEurope, in press
Allison Keys
Allison Keys
Graduate Student
Vyshnavi Vennelakanti
Vyshnavi Vennelakanti
Graduate Student
Ilia Kevlishvili
Ilia Kevlishvili
Postdoctoral Associate
Heather J. Kulik
Heather J. Kulik
Professor of Chemical Engineering and Chemistry