188682-04-4Relevant academic research and scientific papers
Ruthenium-catalyzed cycloisomerization - Oxidation of homopropargyl alcohols. A new access to γ-butyrolactones
Trost, Barry M.,Rhee, Young H.
, p. 11680 - 11683 (1999)
Vinylidenemetal species, which readily form from terminal alkynes under mild conditions, have rarely been utilized as reactive intermediates in a catalytic cycle. The conversion of homopropargyl alcohols via such intermediates to metal-complexed oxacarbenes led to the development of an oxidant compatible with a ruthenium complex capable of performing the cycloisomerization, that would convert them to lactones. None of the oxidants known to stoichiometrically convert isolated metallooxacarbenes to esters are effective. The unconventional oxidants , N-hydroxyimides, proved to be capable of effecting the desired transformation, with N-hydroxysuccinimide being the oxidant of choice. The procedure of choice employs cyclopentadienyl (1,4-cyclooctadiene) ruthenium chloride and trifuryl phosphine as the precatalyst in the presence of tetra-n-butylammonium bromide or hexafluorophosphate with N-hydroxysuccinimide as the oxidant in DMF-water at 95°. In this way, a wide diversity of homopropargyl alcohols were converted to γ-butyrolactones with excellent chemoselectivity. Lactones synthesized include an intermediate toward a platelet aggregation inhibitor, a fruit flavor principle, an inhibitor of binding of phorbol esters to PKC-α, a tobacco constituent, a wood constituent (quercus lactone), an aldosterone antagonist (spironolactone) precursor, and an acetogenin known for pesticidal and antitumor activities (muricatacin).
