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Nickel‐Catalyzed Cyclopropanation with NMe 4 OTf and n BuLi
Author(s) -
Künzi Stefan A.,
Sarria Toro Juan Manuel,
den Hartog Tim,
Chen Peter
Publication year - 2015
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.201505482
Subject(s) - cyclopropanation , diazomethane , nickel , carbene , catalysis , trifluoromethanesulfonate , methylene , chemistry , organometallic chemistry , wittig reaction , reactive intermediate , medicinal chemistry , organic chemistry
Nickel was identified as a catalyst for the cyclopropanation of unactivated olefins by using in situ generated lithiomethyl trimethylammonium triflate as a methylene donor. A mechanistic hypothesis is proposed in which the generation of a reactive nickel carbene explains several interesting observations. Additionally, our findings shed light on a report by Franzen and Wittig published in 1960 that had been retracted later owing to irreproducibility, and provide a rational basis for the systematic development of the reaction for preparative purposes as an alternative to diazomethane or Simmons–Smith conditions.