127231-13-4Relevant articles and documents
A Metallacycle Fragmentation Strategy for Vinyl Transfer from Enol Carboxylates to Secondary Alcohol C-H Bonds via Osmium- or Ruthenium-Catalyzed Transfer Hydrogenation
Park, Boyoung Y.,Luong, Tom,Sato, Hiroki,Krische, Michael J.
, p. 7652 - 7655 (2015)
A strategy for catalytic vinyl transfer from enol carboxylates to activated secondary alcohol C-H bonds is described. Using XPhos-modified ruthenium(0) or osmium(0) complexes, enol carboxylate-carbonyl oxidative coupling forms transient β-acyloxy-oxametallacycles, which eliminate carboxylate to deliver allylic ruthenium(II) or osmium(II) alkoxides. Reduction of the metal(II) salt via hydrogen transfer from the secondary alcohol reactant releases the product of carbinol C-H vinylation and regenerates ketone and zero-valent catalyst.
An approach to α-keto vinyl carbinols
Braun, Marie-Gabrielle,Zard, Samir Z.
, p. 776 - 779 (2011/04/24)
Adducts from the radical addition of xanthates to ethyl vinyl sulfide readily undergo elimination of the xanthate group upon thermolysis to give vinylic and/or allylic sulfides, depending on the structure. In the case of α-xanthyl ketones, the adducts are converted into α-keto vinyl carbinols by rearrangement of the sulfoxides derived from the vinylic and allylic sulfides.
Acid-Catalyzed Ring Expansion of 1-(1-Methoxy-1,2-propadienyl)-2-cyclobuten-1-ols. Synthesis of 5-Hydroxy-5-vinyl-2-cyclopenten-1-ones and Their Stereoselective Transformation to 5-(2-Acetoxyethylidene)-2-cyclopenten-1-ones
Stone, Guy B.,Liebeskind, Lanny S.
, p. 4614 - 4622 (2007/10/02)
The addition of 1-lithio-1-methoxy-1,2-propadiene to various cyclobutenones, cyclobutanones, and benzocyclobutenones produces sensitive 1,2-adducts that, in the presence of acid, rearrange to 5-hydroxy-5-vinyl-2-cyclopenten-1-ones in good to excellent yields.Acid-catalyzed ring expansion of the addition products of 1-lithio-1-methoxy-1,2-propadiene to cyclobutenones bearing a substituent at the 4-position occurs in a stereospecific fashion providing cyclopentenones with the 4-substituent and the 5-hydroxyl group in a cis relationship.After conversion of the 5-hydroxy-5-vinyl- 2-cyclopenten-1-ones to the corresponding allylic acetates, palladium(II)-catalyzed -sigmatropic rearrangement can be effected, furnishing 5-(2-acetoxyethylidene)-2-cyclopenten-1-ones with high kinetic selectivity favoring the isomer with alkylidene substituent and the carbonyl group syn (Z-stereochemistry in most cases).On exposure to a trace of acid, equilibration occurs to the more stable isomer with the alkylidene substituent and carbonyl group anti.
