Premium
C−H Insertion Reactions of Nucleophilic Carbenes
Author(s) -
Arduengo III Anthony J.,
Calabrese J. C.,
Davidson Fredric,
Rasika Dias H. V.,
Goerlich Jens R.,
Krafczyk Roland,
Marshall William J.,
Tamm Matthias,
Schmutzler Reinhard
Publication year - 1999
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/(sici)1522-2675(19991215)82:12<2348::aid-hlca2348>3.0.co;2-m
Subject(s) - chemistry , acetylene , sulfone , adduct , chloroform , acetonitrile , medicinal chemistry , yield (engineering) , insertion reaction , nucleophile , salt (chemistry) , crystal structure , photochemistry , polymer chemistry , organic chemistry , catalysis , materials science , metallurgy
Syntheses and characterizations are described for C−H insertion products derived from 1,3‐dimesityldihydroimidazol‐2‐ylidene ( 1 ) with acetylene, acetonitrile, methyl phenyl sulfone, and chloroform. In the reaction with acetylene, both acetylenic H‐atoms are reactive so that 1 : 1 and 2 : 1 adducts can be obtained. The acetylene and methyl‐phenyl‐sulfone adducts are structurally characterized by means of single‐crystal X‐ray structure determinations. The reactions of 1,3,4,5‐tetramethylimidazolidin‐2‐ylidene ( 8 ) with chloroform or chlorodifluoromethane are shown to yield 2‐(dihaloalkyl)imidazolium salts that arise from a failure of the intermediate 2‐protioimidazolium salt to capture the initially formed halocarbanion.