32569-86-1Relevant academic research and scientific papers
The ketene-surrogate coupling: Catalytic conversion of aryl iodides into aryl ketenes through ynol ethers
Zhang, Wenhan,Ready, Joseph M.
supporting information, p. 8980 - 8984 (2014/11/07)
tert-Butoxyacetylene is shown to undergo Sonogashira coupling with aryl iodides to yield aryl-substituted tert-butyl ynol ethers. These intermediates participate in a [1,5]-hydride shift, which results in the extrusion of isobutylene and the generation of aryl ketenes. The ketenes are trapped in situ with multiple nucleophiles or undergo electrocyclic ring closure to yield hydroxynaphthalenes and quinolines.
Synthesis of alkyl-ynol-ethers by anti-Michael addition of metal alkoxides to β-substituted alkynylsulfones
Marzo, Leyre,Parra, Alejandro,Frias, Maria,Aleman, Jose,Garcia Ruano, Jose Luis
, p. 4405 - 4409 (2013/07/26)
The reaction of metal alkoxides with β-substituted 2-(p-tolylsulfonyl)acetylenes, involving an anti-Michael addition reaction followed by the in situ elimination of the sulfonyl moiety, provides a direct method for the synthesis of alkyl alkynyl ethers bearing aryl or TIPS groups joined to the triple bond. Arylalkynyl ethers derived from primary alkoxides are in situ hydrolyzed into arylacetic esters. Copyright
Transition-metal-free synthesis of aryl-substituted tert-butyl ynol ethers through addition/elimination substitution at an sp centre
Gray, Vincent J.,Slater, Ben,Wilden, Jonathan D.
, p. 15582 - 15585 (2013/01/16)
Nucleophilic attack of an alkoxide on an alkynyl sulfonamide leads to displacement of the sulfonamide at the sp centre and isolation of the ynol ether in good yield in a single operation (see scheme). The mechanistic pathway has been probed by the use of coordinating additives, 13C-labelling experiments and ab initio calculations, which indicated that an addition/elimination mechanism is in operation. Copyright
Synthesis of alkynyl ethers and low-temperature sigmatropic rearrangement of allyl and benzyl alkynyl ethers
Sosa, Juan R.,Tudjarian, Armen A.,Minehan, Thomas G.
supporting information; experimental part, p. 5091 - 5094 (2009/05/31)
(Chemical Equation Presented) α-Alkoxy ketones 3 can be transformed into 1-alkynyl ethers 5 by a two-step procedure involving formation of the enol triflate or phosphate and base-induced elimination. Performing the same reaction sequence with allylic alcohols (R2OH, R2 = allyl) furnishes instead γ,δ-unsaturated carboxylic acid derivatives 6, derived from [3,3]-sigmatropic rearrangement of the intermediate allyl alkynyl ethers at -78 °C and trapping of the subsequently formed ketene with nucleophiles (Nu-H). Benzyl alkynyl ether 5 (R2 = benzyl) rearranges to indanone 7 upon heating to 60 °C.
