Y-Alkoxyketones

Reaction with carbonyl electrophiles is possible, so enantiopure stannanes are excellent precursors of enantiopure a-alkoxy tertiary alcohols [165,167], a-alkoxy acids and esters [180], and a-alkoxyketones [181], and y-alkoxyhydrazides (precur-... 

Markownikoff addition. 2-Methylpent-l-ene allowed to react with tertAmiyl hydroperoxide and mercuric acetate with initial cooling and shaking, after 2 hrs. the volatiles removed by distillation in vacuo, and the residue digested repeatedly with coned, aq. NaCl -> l-diloromercuri-2-tert-butylperoxy-2-methylpentane. Y 19%. F. e., also hydroperoxymercuration with H2 2 s. E. Schmitz, A. Riedie, and O. Brede, J. pr. 312, 30 (1970) a-alkoxyketones from enolesters s. ibid. 312, 43 peroxy- and methoxy-mercuration of a,i -unsatd. ketones and esters s. A. J. Bloodworth and R. J. Bunce, Soc. (C) 1971, 1453. 

Room temperature imidazolium ionic liquids have been shown to be useful solvents for the Michaelis-Arbuzov rearrangement, sometimes allowing the reaction to be performed at room temperature in a short period of tirne. Halolactones, which are the products of halolactonisation of y,5-unsaturated acids, have been shown to be dehalogenated by trialkyphosphites in the presence of water. This makes a useful alternative to the commonly used reduction by tributyltin hydride. The reactions of dibromoethane and dibromopropane with silyl phosphites have been studied. Mono and diphosphonoalkanes (37) and (38) were prepared and their chemical properties were studied. In the reaction of trifluoromethylated P-alkoxyketones with tris(trimethylsilyl)phosphite, a mixture of the 1,2- and 1,4-adducts (39) and (40) is produced. 

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