77202-27-8Relevant academic research and scientific papers
High-Atom Economic Approach to Prepare Chiral α-Sulfenylated Ketones
Margalef, Jèssica,Watile, Rahul A.,Rukkijakan, Thanya,Samec, Joseph S. M.
, p. 11219 - 11227 (2019/09/12)
Chiral α-sulfenylated ketones are versatile building blocks, although there are still several limitations with their preparation. Here we report a new two-step procedure, consisting of Pd-catalyzed hydrothiolation of propargylic alcohols followed by an enantioselective Rh isomerization of allylic alcohols. The isomerization reaction is the key step for obtaining the ketones in their enantioenriched form. The new methodology has a high atom economy and induces good to high levels of enantioselectivity; no waste is produced. A mechanism involving a Rh-hydride-enone intermediate is proposed for the isomerization reaction.
Tandem Pd/Au-catalyzed route to α-sulfenylated carbonyl compounds from terminal propargylic alcohols and thiols
Biswas, Srijit,Watile, Rahul A.,Samec, Joseph S. M.
supporting information, p. 2159 - 2163 (2014/03/21)
An efficient and highly atom-economical tandem Pd/Au-catalyzed route to α-sulfenylated carbonyl compounds from terminal propargylic alcohols and thiols has been developed. This one-step procedure has a wide substrate scope with respect to substituents at
Catalytic adaptive recognition of thiol (SH) and selenol (SeH) groups toward synthesis of functionalized vinyl monomers
Ananikov, Valentine P.,Orlov, Nikolay V.,Zalesskiy, Sergey S.,Beletskaya, Irina P.,Khrustalev, Victor N.,Morokuma, Keiji,Musaev, Djamaladdin G.
experimental part, p. 6637 - 6649 (2012/06/15)
An unprecedented sustainable procedure was developed to produce functionalized vinyl monomers H2C=C(R)(FG) starting from a mixture of sulfur and selenium compounds as a functional group donor (FG = S or Se). The reaction serves as a model for e
Diastereoselective acyclic aza-[2,3] Wittig sigmatropic rearrangements
Anderson, James C.,Smith, Stephen C.,Swarbrick, Martin E.
, p. 1517 - 1521 (2007/10/03)
The scope of anion-stabilising groups in promoting and controlling the diastereoselection of the aza-[2,3] Wittig sigmatropic rearrangement has been assessed by the syntheses of allylic amines 1c-g that have incorporated SiPhMe2, Ph, SPh, SOPh and SO2Ph respectively at the C-2 position. The subsequent anionic [2,3]-sigmatropic rearrangements are analysed with respect to the extent of diastereoselection of the product homoallylic amines 2 and 3. It appears that silicon not only is the most efficient at electronically facilitating this rearrangement, but its steric bulk controls the diastereoselectivity of the process exclusively. Phenyl and phenylthio substituents also have a similar, but decreased, effect on diastereoselection that mirrors their lower steric bulk in comparison to the silicon derivative. Sulfoxide and sulfone substituents are incompatible with the reaction conditions required for rearrangement.
Palladium Catalysis in Allylic Alkylations and Rearrangements in Pyrimidines
Falck-Pedersen, Mette Lene,Benneche, Tore,Undheim, Kjell
, p. 251 - 258 (2007/10/02)
The regiochemistry of the alkylation of 2-pyrimidinones with ?-allylpalladium complexes from allylic acetates and Pd(0) depends on the substitution pattern in the allylic system.In Pd(II)-catalysed rearrangements of 2-propenyloxypyrimidines the preference for a 1,3-rearrangement or the Claisen 3,3-rearrangement is influenced by the substitution pattern in the allylic system.Pd(0) forms ?-allylpalladium complexes with 2-propenyloxypyrimidines which give rise to rearrangement products.The product ratios in the Pd(II) and Pd(0) rearrangements in unsymmetrically substituted allylic systems are different.The rearrangement reactions, especially the Pd(II) rearrangement, give access to products which are difficult to prepare by direct alkylation.
Reactions of 3-(Phenylthio)-3-buten-2-one with Cycloalkanones. A New Approach to Fused Phenols
Takaki, Ken,Okada, Michikazu,Yamada, Michio,Negoro, Kenji
, p. 1200 - 1205 (2007/10/02)
Synthesis and properties of 3-(phenylthio)-3-buten-2-one (7) have been described.The butenone 7 reacted with lithium cycloalkanone enolates to give ketols 14 or diketones 15 in good yields, which were easily transformed into fused phenols 17 by the treatment with p-toluenesulfonic acid or sodium ethoxide, respectively.Oxidative elimination of the sulfenyl group of 14a afforded also 2-naphthol 17a.Tetrahydronaphthalene 23, a key intermediate of calamenene 1a and calamenenal 1b, was successfully synthesized by this approach by starting from l-carvone (19).Bicyclooctanone 25 was obtained in the reaction of 7 with kinetic enolate of 2-cyclohexen-1-one in 84percent yield.
