Blueprints for the Geometric Control of N‐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...
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| Main Authors: | , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2025-07-01
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| Series: | ChemistryEurope |
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| Online Access: | https://doi.org/10.1002/ceur.202500023 |
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| author | Craig S. Day Niklas Grabicki Daniel B. K. Chu Allison Keys Avni Singhal Vyshnavi Vennelakanti Ilia Kevlishvili Rafael Gómez‐Bombarelli Heather J. Kulik Jeremiah Johnson |
| author_facet | Craig S. Day Niklas Grabicki Daniel B. K. Chu Allison Keys Avni Singhal Vyshnavi Vennelakanti Ilia Kevlishvili Rafael Gómez‐Bombarelli Heather J. Kulik Jeremiah Johnson |
| author_sort | Craig S. Day |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-6b59dee673404f4e9d88c73bfd8e4ac8 |
| institution | Matheson Library |
| issn | 2751-4765 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryEurope |
| spelling | doaj-art-6b59dee673404f4e9d88c73bfd8e4ac82025-07-16T10:15:21ZengWiley-VCHChemistryEurope2751-47652025-07-0134n/an/a10.1002/ceur.202500023Blueprints for the Geometric Control of N‐Heterocyclic Carbene–Carbodiimide IsomersCraig S. Day0Niklas Grabicki1Daniel B. K. Chu2Allison Keys3Avni Singhal4Vyshnavi Vennelakanti5Ilia Kevlishvili6Rafael Gómez‐Bombarelli7Heather J. Kulik8Jeremiah Johnson9Department of Chemistry Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USADepartment of Chemistry Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USADepartment of Chemical Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USAProgram in Computational and Systems Biology Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USADepartment of Materials Science and Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USADepartment of Chemistry Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USADepartment of Chemical Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USADepartment of Materials Science and Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USADepartment of Chemistry Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USADepartment of Chemistry Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USARational 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.https://doi.org/10.1002/ceur.2025000233D structurescarbodiimidegeometric controlisomerizationN‐heterocyclic carbineNHC–CDI |
| spellingShingle | Craig S. Day Niklas Grabicki Daniel B. K. Chu Allison Keys Avni Singhal Vyshnavi Vennelakanti Ilia Kevlishvili Rafael Gómez‐Bombarelli Heather J. Kulik Jeremiah Johnson Blueprints for the Geometric Control of N‐Heterocyclic Carbene–Carbodiimide Isomers ChemistryEurope 3D structures carbodiimide geometric control isomerization N‐heterocyclic carbine NHC–CDI |
| title | Blueprints for the Geometric Control of N‐Heterocyclic Carbene–Carbodiimide Isomers |
| title_full | Blueprints for the Geometric Control of N‐Heterocyclic Carbene–Carbodiimide Isomers |
| title_fullStr | Blueprints for the Geometric Control of N‐Heterocyclic Carbene–Carbodiimide Isomers |
| title_full_unstemmed | Blueprints for the Geometric Control of N‐Heterocyclic Carbene–Carbodiimide Isomers |
| title_short | Blueprints for the Geometric Control of N‐Heterocyclic Carbene–Carbodiimide Isomers |
| title_sort | blueprints for the geometric control of n heterocyclic carbene carbodiimide isomers |
| topic | 3D structures carbodiimide geometric control isomerization N‐heterocyclic carbine NHC–CDI |
| url | https://doi.org/10.1002/ceur.202500023 |
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