Blueprints for the Geometric Control of <i>N</i>‐Heterocyclic Carbene–Carbodiimide Isomers
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.
Authors
- Allison M. Keys (ORCID: https://orcid.org/0000-0001-8540-5813)
- Ilia Kevlishvili (ORCID: https://orcid.org/0000-0001-8133-4165)
- Rafael Gómez‐Bombarelli (ORCID: https://orcid.org/0000-0002-9495-8599)
- Craig S. Day (ORCID: https://orcid.org/0000-0002-6931-0280)
- Daniel B. K. Chu (ORCID: https://orcid.org/0000-0002-2427-3906)
- Avni Singhal (ORCID: https://orcid.org/0000-0003-3949-6771)
- Vyshnavi Vennelakanti (ORCID: https://orcid.org/0000-0001-7677-2902)
- Heather Janine Kulik (ORCID: https://orcid.org/0000-0001-9342-0191)
- Niklas Grabicki (ORCID: https://orcid.org/0000-0001-5724-7926)
- Jeremiah Johnson (ORCID: https://orcid.org/0000-0002-3305-0376)
Institutions
- Massachusetts Institute of Technology (US)
Publication Details
- Journal
- ChemistryEurope
- Published
- 2025-04-20
- DOI
- https://doi.org/10.1002/ceur.202500023
- Citations
- 1
- Primary Topic
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.94
Funders
- National Science Foundation
- Novo Nordisk UK Research Foundation
- Deutsche Forschungsgemeinschaft
- Novo Nordisk
- Novo Nordisk Fonden
- Advanced Research Projects Agency
- National Defense Science and Engineering Graduate