Pivotal Synthesis of Tetrasubstituted Epoxides from Ketones and α‐Halo B/Si Ylides with Understanding of the Activation Modes
The epoxidation of ketones with α‐monohalo borylsilylmethane reagents renders tetrasubstituted epoxides, opening a new reactive pathway by supression of Boron‐Wittig or Peterson olefination pathways. This method enables the preparation of novel 1,1,2,2‐tetrasubstituted borosilylepoxides with intrinsic control of the diastereoselectivity. A mechanism, based on density functional theory calculations, has been postulated analyzing the role of the α‐iodo B, Si‐ylide in the cyclization pathway. Complementarily, enolates generated from ketones can also interact with the α‐monohalo diborylsilylmethane reagents to acceed the 1,1,2,2‐tetrasubstituted borosilylepoxides. The versatility of these entities has been demonstrated through postfunctionalization reactions.
Authors
- Paula Dominguez‐Molano (ORCID: https://orcid.org/0000-0001-9735-5008)
- Feliu Maseras (ORCID: https://orcid.org/0000-0001-8806-2019)
- Lucía Morán‐González (ORCID: https://orcid.org/0000-0002-5898-7093)
- Oriol Salvadó (ORCID: https://orcid.org/0000-0002-3493-8211)
- Elena Fernández (ORCID: https://orcid.org/0000-0001-9025-1791)
- Edmond Apaloo‐Messan (ORCID: https://orcid.org/0009-0003-0192-503X)
- Manuel Rodríguez (ORCID: https://orcid.org/0009-0003-3690-9849)
- Luis Tarifa
- Stanley Wilkinson
Institutions
- Institut Català d'Investigació Química (ES)
- Institut Català d'Arqueologia Clàssica (ES)
- Universitat Rovira i Virgili (ES)
Publication Details
- Journal
- ChemistryEurope
- Published
- 2025-09-15
- DOI
- https://doi.org/10.1002/ceur.202500241
- Citations
- 2
- Primary Topic
- Catalytic C–H Functionalization Methods
- Type
- article
- Field-Weighted Citation Impact
- 1.87
Funders
- Ministerio de Ciencia, Innovación y Universidades
- Centres de Recerca de Catalunya
- Generalitat de Catalunya
- European Regional Development Fund
- Agencia Estatal de Investigación