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Sydnone Methides—A Forgotten Class of Mesoionic Compounds for the Generation of Anionic N‐Heterocyclic Carbenes
Author(s) -
Mummel Sebastian,
Lederle Felix,
Hübner Eike G.,
Namyslo Jan C.,
Nieger Martin,
Schmidt Andreas
Publication year - 2021
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.202107495
Subject(s) - chemistry , sydnone , carbene , mesoionic , deprotonation , adduct , nuclear magnetic resonance spectroscopy , medicinal chemistry , photochemistry , organic chemistry , catalysis , ion , ring (chemistry)
Sydnone methides are described from which only one single example has been mentioned in the literature so far. Their deprotonation gave anions which can be formulated as π‐electron rich anionic N‐heterocyclic carbenes. Sulfur and selenium adducts were stabilized as their methyl ethers, and mercury, gold as well as rhodium complexes of the sydnone methide carbenes were prepared. Sydnone methide anions also undergo C−C coupling reactions with 1‐fluoro‐4‐iodobenzene under Pd(PPh 3 ) 4 and CuBr catalysis. 77 Se NMR resonance frequencies and 1 J C4‐Se as well as 1 J C4‐H coupling constants have been determined to gain knowledge about the electronic properties of the anionic N‐heterocyclic carbenes. The carbene carbon atom of the sydnone methide anion 3 j resonates at δ =155.2 ppm in 13 C NMR spectroscopy at −40 °C which is extremely shifted upfield in comparison to classical N‐heterocyclic carbenes.