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PreprintCC BYChemRxiv

Origin of Reagent-Dependent Diastereoselectivity in Grignard Additions to a TADDOL-Derived α-Ketiminophosphonate

  • Adrián López-Francés1,2
  • Javier Vicario1
  • Abel de Cózar3,4
4 affiliations
  1. 1Department of Organic Chemistry I, Faculty of Pharmacy, University of the Basque Country, UPV/EHU, Paseo de la Universidad 7, Vitoria-Gasteiz, Spain, 01006
  2. 2Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, United Kingdom, OX1 3TA
  3. 3Ikerbasque, Basque Foundation for Science, Plaza Euskadi 5, Bilbao, Spain, 48009
  4. 4Department of Organic Chemistry I, Donostia International Physics Centre (DIPC, UPV/EHU, Paseo Manuel de Lardizabal, 3, Donostia-San Sebastián, Spain, 20018
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Abstract

Grignard additions to a TADDOL-derived -ketiminophosphonate display pronounced reagent-dependent diastereoselectivity, with dr values of 94:6 for methylmagnesium bromide and 55:45 for 2-naphthylmagnesium bromide. In this study, we carried out DFT calculations showing that dimeric Grignard models coordinate to the phosphoryl and sulfonyl regions of the substrate, restricting C–P bond rotation and enabling facial differentiation. The nature of the Grignard reagent modulates the organisation of the reactive complex and the relative stability of the competing transition structures, providing a mechanistic rationale for the contrasting stereochemical

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Cite

BibTeXRIS
BibTeX
@misc{lopezfrances2026origin,
  title = {{Origin of Reagent-Dependent Diastereoselectivity in Grignard Additions to a TADDOL-Derived α-Ketiminophosphonate}},
  author = {Adrián López-Francés and Javier Vicario and Abel de Cózar},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009360/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009360/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Origin of Reagent-Dependent Diastereoselectivity in Grignard Additions to a TADDOL-Derived α-Ketiminophosphonate
AU  - Adrián López-Francés
AU  - Javier Vicario
AU  - Abel de Cózar
PY  - 2026
DA  - 2026/09/23
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009360/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009360/v1
AB  - Grignard additions to a TADDOL-derived -ketiminophosphonate display pronounced reagent-dependent diastereoselectivity, with dr values of 94:6 for methylmagnesium bromide and 55:45 for 2-naphthylmagnesium bromide. In this study, we carried out DFT calculations showing that dimeric Grignard models coordinate to the phosphoryl and sulfonyl regions of the substrate, restricting C–P bond rotation and enabling facial differentiation. The nature of the Grignard reagent modulates the organisation of the reactive complex and the relative stability of the competing transition structures, providing a mechanistic rationale for the contrasting stereochemical
ER  -