49764-18-3Relevant articles and documents
Oxidative alkylation of azoles: VII. Adamantylation of azoles via oxidative generation of 1-adamantyl cations
Tsypin,Pevzner,Golod
, p. 1762 - 1766 (2001)
A procedure has been developed for oxidative N-adamantylation of azoles with 1-iodoadamantane in the presence of chromium(IV) oxide or iodine(V) oxide. The procedure is applicable to azoles whose pKBH+ value does not exceed 2.26. * For communication VI, see [1].
Carbocation-forming reactions in ionic liquids
Creary, Xavier,Willis, Elizabeth D.,Gagnon, Madeleine
, p. 18114 - 18120 (2007/10/03)
A number of trifluoroacetates, mesylates, and triflates have been studied in ionic liquids. Several lines of evidence indicate that all of these substrates react via ionization to give carbocationic intermediates. For example, cumyl trifluoroacetates give mainly the elimination products, but the Hammett ρ+ value of -3.74 is consistent with a carbocationic process. The analogous exo-2-phenyl-endo-3-deutero-endo-bicyclo-[2.2.1]hept-2-yl trifluoroacetate gives an elimination where loss of the exo-hydrogen occurs from a cationic intermediate. 1-Adamantyl mesylate and 2-adamantyl triflate react to give simple substitution products derived from capture of 1- and 2-adamantyl carbocations by the residual water in the ionic liquid. The triflate derivative of pivaloin, trans-2-phenylcyclopropylcarbinyl mesylate, 2,2-dimethoxycyclobutyl triflate, the mesylate derivative of diethyl (phenylhydroxymethyl)-thiophosphonate, and Z-1-phenyl-5-trimethylsilyl-3-penten- 1-yl trifluoroacetate all give products derived carbocation rearrangements (kΔ processes), anti-7-Norbornenyl mesylate gives products with complete retention of configuration, indicative of involvement of the delocalized 7-norbornenyl cation. 1,6-Methano[10]annulen-11-yl triflate reacts in [BMIM][NTf2] to give 1,6-methano[10]annulen-11-ol, along with naphthalene, an oxidized product derived from loss of trifluoromethanesulfinate ion. Analogous loss of CF3SO2- can be seen in reaction of PhCH(CF3)OTf. Ionic liquids are therefore viable solvents for formation of carbocationic intermediates via kc and k Δ processes.
Reactions of copper(II) β-diketonates under free radical conditions. Preparation of highly congested β-diketones
Lloris, Maria E.,Galvez, Nicanor,Marquet, Jorge,Moreno-Manas, Marcial
, p. 8031 - 8042 (2007/10/02)
Copper(II) β-diketonates react with alkyl bromides under free radical conditions to give highly congested β-diketones such as 3-(1-adamantyl)-3-alkylpentane-2,4-diones. Another typical free radical reagent: benzoyl peroxide, reacts also functionalizing the intercarbonyl positions.
Alxylations of α-methyl substituted β-diketones throught their Cu(II) complexes. Preparation of sterically congested β-diketones
Lloris, Maria E.,Marquet, Jorge,Moreno-Manas, Marcial
, p. 7489 - 7492 (2007/10/02)
The copper(II) complexes of 3-methylpentane-2,4-dione and 2-methyl-1-phenylbutane-1,3-dione are good substrates for C-alkylation with several alkyl bromides including 1-bromoadamantane and 9-bromofluorene. Sterically congested β-diketones have been prepared.
