3720-20-5Relevant academic research and scientific papers
New strategies in carbonylation chemistry: The synthesis of δ-lactones from saturated alcohols and CO
Tsunoi, Shinji,Ryu, Ilhyong,Okuda, Tohru,Tanaka, Minoru,Komatsu, Mitsuo,Sonoda, Noboru
, p. 8692 - 8701 (2007/10/03)
This paper describes the δ-carbonylation of saturated alcohols which uses a 1,5-hydrogen-transfer reaction of alkoxyl radicals and subsequent carbonylation at the δ-carbon atoms as the key. The carbonylation reactions of five classes of saturated alcohols, namely, primary alcohols having primary δ-carbons, primary alcohols having secondary δ-carbons, primary alcohols having tertiary δ-carbons, secondary alcohols having primary δ- carbons, secondary alcohols having secondary δ-carbons, were carded out, in which lead tetraacetate (LTA) was used as a one-electron oxidant to generate the alkoxyl radicals. Carbonylation of these saturated alcohols, except for primary alcohols having tertiary δ-carbons, took place to afford δ-lactones in moderate to good yields. The mechanism of the remote carbonylation likely involves (1) alkoxyl radical generation via LTA oxidation of a saturated alcohol, (2) conversion of this alkoxyl radical to a δ-hydroxyalkyl radical by a 1,5-hydrogen-transfer reaction, (3) CO trapping of the δ-hydroxyalkyl radical yielding an acyl radical, and (4) oxidation and cyclization of the acyl radical to give a δ-lactone. A metal salt-free system was also tested for a substrate derived from a tertiary alcohol having a secondary δ- carbon; the photolysis of an alkyl 4-nitrobenzenesulfenate under CO pressures gave a δ-lactone in moderate yield.
