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Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Non‐Innocent Reaction Medium
Author(s) -
Dilauro Giuseppe,
Dell'Aera Marzia,
Vitale Paola,
Capriati Vito,
Perna Filippo Maria
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201705412
Subject(s) - chemistry , protonolysis , nucleophile , catalysis , solvent , nucleophilic addition , organic chemistry , organometallic chemistry , organic synthesis , photochemistry
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.