204381-85-1Relevant academic research and scientific papers
Oxidative homologation of aldehydes to α-ketoaldehydes by using iodoform, o-iodoxybenzoic acid, and dimethyl sulfoxide
Zall, Andrea,Bensinger, Dennis,Schmidt, Boris
experimental part, p. 1439 - 1447 (2012/04/04)
An efficient three-step synthetic route to α-ketoaldehydes starting from aryl aldehydes is reported. The aldehydes were treated with iPrMgCl and iodoform to obtain β-diiodoalcohols, which were then oxidized with o-iodoxybenzoic acid at room temperature to the corresponding β-diiodoketones. Subsequent reaction of the β-diiodoketone to the α-ketoaldehyde occurred under oxygen transfer from dimethyl sulfoxide. These sensitive products were in situ cyclized with o-phenylenediamine to form the stable monosubstituted quinoxalines, which could be characterized and isolated easily. α-Ketoaldehydes are a versatile, highly reactive moiety for the synthesis of heterocyclic compounds. We investigated the transformation of aldehydes into α-ketoaldehydes via β-diiodoketone intermediates and finally applied the procedure to the synthesis of peptidic substrates. Copyright
Synthesis of (E)-α,β-unsaturated esters and (Z)-vinyl halides with total or high diastereoselectivity by using samarium metal
Concellon, Jose M.,Rodriguez-Solla, Humberto,Huerta, Monica,Perez-Andres, Juan A.
, p. 1839 - 1847 (2007/10/03)
A highly diastereoselective β-elimination of 2-halo-3-hydroxy esters 1 or O-acetylated 1,1-dihaloalkan-2-ols 4 is achieved with samarium in the presence of diiodomethane, yielding α,β-unsaturated esters 2 or vinyl halides 5, respectively. The β-elimination reaction was promoted by samarium diiodide, which was generated in situ. The starting halohydrins 1 or 4 are easily prepared by reaction of the corresponding lithium enolates of α-halo esters or dihalomethyllithium with aldehydes at -78°C. The influence of the reaction conditions and the structure of the starting compounds on the diastereoselectivity of the β-elimination reactions is discussed, A comparative study of the β-elimination reaction with preformed SmI2 and metallic samarium is also performed. These elimination reactions can be explained by the proposed mechanism. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002).
Samarium diiodide-promoted diiodomethylation of carbonyl compounds with iodoform. Synthetic applications of diiodoalcohols
Concellon, Jose M.,Bernad, Pablo L.,Perez-Andres, Juan A.
, p. 1409 - 1412 (2007/10/03)
A rapid and effective diiodomethylation of carbonyl compounds using SmI2 and iodoform is described. Transformations of the obtained diiodoalcohols 2 into α-iodoaldehydes 5 and α-hydroxyacids 6 is also reported.
