| Title: | Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Non-Innocent Reaction Medium |
| Author(s): | Dilauro G; Dell'Aera M; Vitale P; Capriati V; Perna FM; |
| Address: | "Dipartimento di Farmacia-Scienze del Farmaco, Universita di Bari 'A. Moro', Consorzio C.I.N.M.P.I.S., Via E. Orabona 4, I-70125, Bari, Italy" |
| ISSN/ISBN: | 1521-3773 (Electronic) 1433-7851 (Linking) |
| Abstract: | "In contrast to classic methods carried out under inert atmospheres with dry volatile organic solvents and often low temperatures, 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. Secondary amines and tertiary carbinamines are furnished in yields of up to and over 99 %. The significant solvent D/H isotope effect observed for the on-water nucleophilic additions of organolithium compounds 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 disfavoring 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" |
| Keywords: | Grignard reagents azo compounds nucleophilic addition organolithium compounds water chemistry; |
| Notes: | "PubMed-not-MEDLINEDilauro, Giuseppe Dell'Aera, Marzia Vitale, Paola Capriati, Vito Perna, Filippo Maria eng Research Support, Non-U.S. Gov't Germany 2017/07/12 Angew Chem Int Ed Engl. 2017 Aug 14; 56(34):10200-10203. doi: 10.1002/anie.201705412. Epub 2017 Jul 26" |
