Synthesis, Structure, and Properties of Amino-Substituted Benzhydrylium Ions – A Link between Ordinary Carbocations and Neutral Electrophiles
Optimized synthetic procedures for the straightforward access to eleven amino-substituted diarylmethylium tetrafluoroborates are described. These benzhydrylium ions cover a range of seven orders of magnitude in electrophilicity and provide a link between ordinary carbocations and neutral electrophiles. Five of these highly stabilized benzhydrylium tetrafluoroborates were characterized by single-crystal X-ray crystallography. While the experimentally determined bond lengths and angles in the solid state perfectly agree with those calculated by DFT methods for the gas phase and aqueous solution, crystal packing accounts for large differences in the twist angles of the aryl groups found in the solid state as compared to calculated structures.
Mayer, Robert J.,Hampel, Nathalie,Mayer, Peter,Ofial, Armin R.,Mayr, Herbert
supporting information
p. 412 - 421
(2018/09/14)
Nickel(0)/N-heterocyclic carbene complexes catalysed arylation of aromatic diamines
Nickel complexes of N-heterocyclic carbenes were examined for effecting C-N coupling reactions between aromatic diamines and aryl chlorides of varying electron density. The Ni(0) ? 2IPr (IPr = N,N′-bis(2,6- diisopropylphenyl)imidazol-2-ylidene) complex associated to t-BuONa allowed N,N′-diarylation at 100 °C in 1,4-dioxane with excellent yields. Selective monoarylation of diamines could be performed in THF at 65 °C.
Kuhl, Sébastien,Fort, Yves,Schneider, Rapha?l
p. 6169 - 6177
(2007/10/03)
Alkylidene Transfer from Monochloroalkylmercury(II) Compounds to Aromatic Amines; Selective C-Alkylation
αα-Diarylalkane derivatives have been synthesized from monochloroalkylmercury(II) compounds in a noncarbenoid alkylidene transfer reaction which takes place selectively on the aromatic ring.A mechanism is suggested for this process.Intermediate products are prepared by alternative routes to ascertain their participation in the course of the reaction.As a consequence, two different aryl groups can be successively incorporated into the alkane molecule.
Barluenga, Jose,Campos, Pedro J.,Roy, Miguel A.,Asensio, Gregorio
p. 1420 - 1426
(2007/10/02)
PHOTOCHEMICAL STUDIES ON AN AROMATIC AMINE - METHANE POLYCHLORO DERIVATIVE SYSTEM. PART VIII. PHOTOCHEMICAL ACTIVITY OF SOME ANILINE AND PHENOL DERIVATIVES IN DICHLOROMETHANE AND IN A MIXTURE OF DICHLOROMETHANE WITH BENZENE