Espinosa-Jalapa, Noel Angel and Kumper, Manuel and Bauer, Jonathan O. (2025) CO2 Unlocks Reactivity: Boryl Silyl Ketene Acetals Enable Mild and Direct C=C Bond Cleavage. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 147 (51). pp. 47573-47583. ISSN 0002-7863, 1520-5126
Full text not available from this repository. (Request a copy)Abstract
Boron-ligand cooperation (BLC) has emerged as a powerful principle of bond activation with main-group elements, yet pyridine-based systems have so far eluded experimental evidence of CO2 activation. We show here that four-membered pyridyl-boracycles activate CO2 through a dearomatizing boron-carbon bond cleavage, unambiguously proceeding by a BLC rather than a B/N-FLP-type mechanism, as confirmed by density functional theory (DFT) studies, in contrast to previously predicted computational pathways. This process furnishes boryl silyl ketene acetals, a hitherto unknown class of enolate equivalents in which the two oxygen atoms are differentiated by boryl and silyl substituents. These intermediates exhibit remarkable follow-up reactivity, eventually leading to a mild, one-step C=C double-bond cleavage that delivers fulvene derivatives under additive-free conditions, thereby constituting an unprecedented form of metathesis. Overall, our findings establish boryl silyl ketene acetals derived from CO2 as a novel class of main-group systems that unlock a reactivity platform with far-reaching synthetic implications.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | METAL-LIGAND-COOPERATION; DIELS-ALDER REACTIONS; MUKAIYAMA ALDOL REACTION; CARBON-DIOXIDE; MAIN-GROUP; CATALYTIC-REDUCTION; BASIS-SETS; X-RAY; ACTIVATION; DIHYDROGEN; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 16 Jun 2026 09:41 |
| Last Modified: | 16 Jun 2026 09:41 |
| URI: | https://pred.uni-regensburg.de/id/eprint/66157 |
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