In contrast to classic protocols carried out under inert atmospheres with dry volatile organic solvents and often low temperatures, we report that the addition of highly polar organometallic compounds to non-activated imines and nitriles proceeds quickly, efficiently, and chemoselectively with a broad range of substrates at room temperature and under air with water as the only reaction medium, providing secondary amines and tertiary carbinamines with yields up to >99%. The significant solvent D/H isotope effect observed for the on-water nucleophilic additions of organolithiums to imines suggests that the on-water catalysis arises from proton transfer across the organic-water interface. The strong intermolecular hydrogen bonds between water molecules may play a key role in disfavouring protonolysis, which occurs extensively in other protic media such as methanol. This work lays the foundation for reshaping many fundamental s-block metal-mediated organic transformations in water.

Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Non-Innocent Reaction Medium

DILAURO, GIUSEPPE;DELL'AERA, MARZIA;VITALE, PAOLA;CAPRIATI, Vito;PERNA, FILIPPO
2017-01-01

Abstract

In contrast to classic protocols carried out under inert atmospheres with dry volatile organic solvents and often low temperatures, we report that the addition of highly polar organometallic compounds to non-activated imines and nitriles proceeds quickly, efficiently, and chemoselectively with a broad range of substrates at room temperature and under air with water as the only reaction medium, providing secondary amines and tertiary carbinamines with yields up to >99%. The significant solvent D/H isotope effect observed for the on-water nucleophilic additions of organolithiums to imines suggests that the on-water catalysis arises from proton transfer across the organic-water interface. The strong intermolecular hydrogen bonds between water molecules may play a key role in disfavouring protonolysis, which occurs extensively in other protic media such as methanol. This work lays the foundation for reshaping many fundamental s-block metal-mediated organic transformations in water.
File in questo prodotto:
File Dimensione Formato  
2017 ANIE RLi water.pdf

non disponibili

Tipologia: Documento in Versione Editoriale
Licenza: NON PUBBLICO - Accesso privato/ristretto
Dimensione 605.08 kB
Formato Adobe PDF
605.08 kB Adobe PDF   Visualizza/Apri   Richiedi una copia
2017 Synfact, highlighted.pdf

non disponibili

Tipologia: Documento in Versione Editoriale
Licenza: NON PUBBLICO - Accesso privato/ristretto
Dimensione 472.33 kB
Formato Adobe PDF
472.33 kB Adobe PDF   Visualizza/Apri   Richiedi una copia
2017_ANIE_ms_finale.pdf

Open Access dal 11/08/2018

Descrizione: Articolo post print accesso pubblico
Tipologia: Documento in Post-print
Licenza: Creative commons
Dimensione 2.29 MB
Formato Adobe PDF
2.29 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11586/197847
Citazioni
  • ???jsp.display-item.citation.pmc??? 11
  • Scopus 86
  • ???jsp.display-item.citation.isi??? 81
social impact