646516-60-1Relevant academic research and scientific papers
A robust and general protocol for the Lewis-base-catalysed reaction of alcohols and alkyl propiolates
Tejedor, David,Alvarez-Mendez, Sergio J.,Lopez-Soria, Juan M.,Martin, Victor S.,Garcia-Tellado, Fernando
, p. 198 - 205 (2014/01/06)
A general and practical protocol for the tertiary-amine-catalysed synthesis of β-alkoxyacrylates from primary, secondary, and tertiary alcohols is described. Of the currently used catalysts, DABCO proved to be the best one for this process. Three factors seem to influence the outcome of the reaction: (1) the nucleophilic strength of the catalyst, (2) the electrophilicity of the intermediate ammonium acrylate, and (3) the pKa/nucleophilicity of the alcohol/alkoxide nucleophile. Reactivity tuning enables the transformation of a range of tertiary alcohols into the corresponding β-alkoxyacrylate derivatives. Differences in the reactivity of different types of alcohol allow the selective transformation of diols containing two different hydroxy groups into the corresponding monoprotected derivatives. This protocol will aid other synthetic organic chemists to easily prepare such vinyl ethers under atom-economic, efficient, and bench-friendly reaction conditions. A practical protocol for the DABCO-catalysed synthesis of β-alkoxyacrylates is described. The protocol is efficient and economical, and it allows the transformation of a range of alcohols (including tertiary alcohols) into the corresponding β-alkoxyacrylate derivatives and the selective monoprotection of different diols (primary vs. secondary and tertiary). Copyright
Remote stereocontrol in [3,3]-sigmatropic rearrangements: Application to the total synthesis of the immunosuppressant mycestericin G
Fairhurst, Nathan W. G.,Mahon, Mary F.,Munday, Rachel H.,Carbery, David R.
supporting information; experimental part, p. 756 - 759 (2012/03/26)
The Ireland - Claisen [3,3]-sigmatropic rearrangement has been used to access biologically important β,β′-dihydroxy α-amino acids. The rearrangement reported is highly stereoselective and offers excellent levels of remote stereocontrol. This strategy has been used to synthesize the natural immunosuppressant mycestericin G and ent-mycestericin G, allowing for a revision of absolute configuration of this natural product.
Samarium(II) promoted stereoselective synthesis of antiproliferative cis-β-alkoxy-γ-alkyl-γ-lactones
Donadel, Osvaldo J.,Martin, Tomas,Martin, Victor S.,Padron, Jose M.
, p. 18 - 21 (2007/10/03)
Samarium(II) iodide promotes the stereoselective synthesis of cis-β-alkoxy-γ-alkyl-γ-lactones under mild conditions starting from linear precursors. The in vitro antiproliferative activities were examined in the human solid tumor cell lines from diverse origin A2780, SW1573, and WiDr. From the growth inhibition data a structure-activity relationship was obtained. Overall the results point to the relevant role of cis-β-alkoxy-γ-alkyl-γ-lactones as novel scaffolds for the development of new anticancer drugs.
β-Sulfinyl acrylate esters as a convenient source of alkane- and arenesulfenate anions
O'Donnell, Jennifer S.,Schwan, Adrian L.
, p. 6293 - 6296 (2007/10/03)
Methyl acrylate esters bearing alkane- and arenesulfinyl units on the 2-carbon liberate sulfenate anions upon nucleophilic attack. The sulfenates are readily captured through sulfur alkylation. When a sulfenate derived from R-cysteine is generated, diastereoselective benzylation is observed.
Stereospecific Grignard reactions of cholesteryl 1-alkenesulfinate esters: Application of the Andersen protocol to the preparation of non-racemic α,β-unsaturated sulfoxides
Strickler, Rick R.,Motto, John M.,Humber, Craig C.,Schwan, Adrian L.
, p. 423 - 430 (2007/10/03)
Enantiomerically enriched α,β-unsaturated sulfinate esters of (-)-cholesterol undergo stereospecific substitutions at sulfur when treated in benzene at 6°C with Grignard reagents. Sulfoxides with ees of 85-99.5% are obtained when enantiopure sulfinates are used. The substitution reactions proceed with inversion of sulfur configuration. Enantiomerically pure cholesteryl (E)-2-carbomethoxyethenesulfinate is not a suitable reactant under the Grignard reaction conditions. It is suggested that the ester group induces unwanted reactions significantly lowering both the yield and sulfur stereogenicity.
