69849-30-5Relevant academic research and scientific papers
Reinvestigation of the synthetic and mechanistic aspects of Mn(III) acetate mediated oxidation of enones
Demir, Ayhan S.,Reis, ?mer,Igdir, A. Cigdem
, p. 3427 - 3432 (2004)
Mn(OAc)3 mediated α′-acetoxylation of α,β-unsaturated enones is reinvestigated from a synthetic and mechanistic point of view and an improved procedure based on the use of acetic acid as a co-solvent is presented. Excellent results were obtained for a variety of structurally diverse and synthetically important enones under the optimized conditions.
Synthesis of cyclopentenones via intramolecular HWE and the palladium-catalyzed reactions of allylic hydroxy phosphonate derivatives
Yan, Bingli,Spilling, Christopher D.
, p. 5385 - 5396 (2008/12/21)
(Chemical Equation Presented) Palladium-catalyzed decarboxylative rearrangement of nonracemic phosphono allylic acetoacetates, or the intermolecular allylic substitution of nonracemic phosphono allylic carbonates with tert-butyl acetoacetate followed by h
Three-Carbon Annelations. Regiocontrolled Reactivity of Trimethylsilyl- and Ethoxyethyl-Protected Cyanohydrins. Versatile Homoenolate and Acyl Anion Equivalents
Jacobson, Richard M.,Lahm, George P.,Clader, John W.
, p. 395 - 405 (2007/10/02)
The trimethylsilyl- (2) and ethoxyethyl- (4) protected cyanohydrins of α,β-unsaturated aldehydes are utilized as three-carbon annelation reagents.Metalated reagent 2 displays exclusive α reactivity with aldehydes and ketones at -78 deg C.Metalated reagent 4 displays exclusive α reactivity at -78 deg C and exclusive γ reactivity at 0 deg C.Reagent 4 thus allows for complete regiocontrol in its addition to aldehydes and ketones which permits selective addition of either a homoenolate or an acyl anion equivalent.Metalation of the α product 11 at -78 deg C with subsequent warming to 0 deg C produces exclusively the γ product, confirming the reversible nature of the addition to the carbonyl.The derived α '-trimethylsiloxy enones 17 (R3=Me3Si), α '-hydroxy enones 17 (R3=H), α '-acetoxyenones 17 (R3=Ac), and γ-lactones 10 are useful cyclopentenone precursors.Treatment of 17 with p-TsOH in toluene at reflux produces cyclopentenones.The reaction proceeds via the postulated intermediacy of a pentadienyl cation 15 which undergoes in situ electrocyclic ring closure.
