Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Non‐Innocent Reaction Medium. Issue 34 (26th July 2017)

• Record Type: Journal Article
• Authors: Dilauro, Giuseppe; Dell'Aera, Marzia; Vitale, Paola; Capriati, Vito; Perna, Filippo Maria
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 34(2017)
• Page Start: 10200
• Page End: 10203
• Publication Date: 2017-07-26
• Subjects: azo compounds -- Grignard reagents -- nucleophilic addition -- organolithium compounds -- water chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201705412
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : Symphony between RLi and water : Unprecedented access to secondary amines and tertiary carbinamines from imines and nitriles using highly polar organometallic compounds and with water as the only reaction medium was achieved in very good yields. These reactions proceed quickly, smoothly, and chemoselectively at room temperature and under air.