1.Protected glycosides and disaccharides of 2-amino-2-deoxy-D-glucopyranose by ferric chloride-catalyzed coupling.
Kiso M, Anderson L. Carbohydr Res. 1985 Feb 28;136:309-23.
The ferric chloride-catalyzed glycosylation of hydroxy compounds by protected 2-acylamino-2-deoxy-beta-D-glucopyranose 1-acetates is described. In addition to known glycosides from the reaction of alcohols with 2-acetamido-1,3,4,6-tetra-O-acetyl-2-deoxy-beta-D-glucopyranose (3), ally (and other alkyl) beta-glycosides were obtained from the N-benzoyl, N-phenoxyacetyl, N-methoxyacetyl, N-chloroacetyl, and N-phthaloyl congeners of 3. The latter compounds, except for the N-phthaloyl derivative, gave oxazolines in the absence of an alcoholic reactant. Compound 3 and the related N-benzoyl, N-chloroacetyl, N-acetyl-3,4,6-tri-O-benzyl, and N-acetyl-4-O-acetyl-3,6-di-O-benzyl derivatives were coupled to one or more protected sugars to form protected, beta-linked disaccharides. Coupling at the 6-positions of acceptors proceeded smoothly and gave 67-80% yields. For successful coupling at positions 3 and 4, long reaction times and multiple additions of glycosyl donor were required, and yields ranged from 60% to as low as 30%.
2.Electrophilic Aromatic Substitution. 13.(1) Kinetics and Spectroscopy of the Chloromethylation of Benzene and Toluene with Methoxyacetyl Chloride or Chloromethyl Methyl Ether and Aluminum Chloride in Nitromethane or Tin Tetrachloride in Dichloromethane. The Methoxymethyl Cation as a Remarkably Selective Common Electrophile.
DeHaan FP1, Djaputra M, Grinstaff MW, Kaufman CR, Keithly JC, Kumar A, Kuwayama MK, Macknet KD, Na J, Patel BR, Pinkerton MJ, Tidwell JH, Villahermosa RM. J Org Chem. 1997 May 2;62(9):2694-2703.
Vacuum line kinetics studies have been made of the reaction in nitromethane between benzene and/or toluene, methoxyacetyl chloride (MAC), and AlCl(3) to produce benzyl or xylyl chlorides, CO, and a CH(3)OH(-)AlCl(3) complex. For both arenes, the rate law appears to be R = (k(3)/[AlCl(3)](0)) [AlCl(3)](2)[MAC]. When chloromethyl methyl ether (CMME) is substituted for MAC, a similar rate law is obtained. Both chloromethylation reactions yielded similar, large k(T)()/k(B)() ratios (500-600) and similar product isomer distributions with low meta percentages ( approximately 0.4) which suggest CH(3)OCH(2)(+) or the CH(3)OCH(2)(+)Al(2)Cl(7)(-) ion pair as a common, remarkably selective, electrophile. The kinetics of MAC decomposition to CMME and CO in the presence of AlCl(3) yielded the rate law R = k(2)[AlCl(3)](0)[MAC]. Here AlCl(3) is a catalyst (no CH(3)OH is formed), and thus the rate law is equivalent to the chloromethylation rate law. All three reactions have comparable reactivities, which is consistent with rate-determining production of the electrophile.