90458-77-8Relevant academic research and scientific papers
Intramolecular OH...Fluorine Hydrogen Bonding in Saturated, Acyclic Fluorohydrins: The γ-Fluoropropanol Motif
Linclau, Bruno,Peron, Florent,Bogdan, Elena,Wells, Neil,Wang, Zhong,Compain, Guillaume,Fontenelle, Clement Q.,Galland, Nicolas,Le Questel, Jean-Yves,Graton, Jér?me
supporting information, p. 17808 - 17816 (2015/12/08)
Fluorination is commonly exercised in compound property optimization. However, the influence of fluorination on hydrogen-bond (HB) properties of adjacent functional groups, as well as the HB-accepting capacity of fluorine itself, is still not completely understood. Although the formation of OH...F intramolecular HBs (IMHBs) has been established for conformationally restricted fluorohydrins, such interaction in flexible compounds remained questionable. Herein is demonstrated for the first time - and in contrast to earlier reports - the occurrence of OH...F IMHBs in acyclic saturated γ-fluorohydrins, even for the parent 3-fluoropropan-1-ol. The relative stereochemistry is shown to have a crucial influence on the corresponding h1JOH...F values, as illustrated by syn- and anti-4-fluoropentan-2-ol (6.6 and 1.9 Hz). The magnitude of OH...F IMHBs and their strong dependence on the overall molecular conformational profile, fluorination motif, and alkyl substitution level, is rationalized by quantum chemical calculations. For a given alkyl chain, the "rule of shielding" applies to OH...F IMHB energies. Surprisingly, the predicted OH...F IMHB energies are only moderately weaker than these of the corresponding OH...OMe. These results provide new insights of the impact of fluorination of aliphatic alcohols, with attractive perspectives for rational drug design.
Palladium-catalyzed selective anti-markovnikov oxidation of allylic esters
Dong, Jia Jia,Fananas-Mastral, Martin,Alsters, Paul L.,Browne, Wesley R.,Feringa, Ben L.
, p. 5561 - 5565 (2013/06/27)
An aldol alternative: The palladium(II)-catalyzed anti-Markovnikov oxidation of allylic esters to aldehydes at room temperature provides a viable alternative to valuable cross aldol products. High regioselectivity towards the aldehyde product was achieved using the ester protecting group for the allylic alcohol. Rapid isomerization and the much higher rate of oxidation of the branched isomer result in the same product forming from both linear and branched allylic esters. Copyright
Lewis acid-promoted addition of 1,3-bis(silyl)propenes to aldehydes: A route to 1,3-dienes
Borg, Tessie,Tuzina, Pavel,Somfai, Peter
, p. 8070 - 8075 (2011/11/28)
The Lewis acid-promoted addition of 1,3-bis(silyl)-propenes to aldehydes to provide the corresponding (E)-1,3-dienes in excellent stereoselectivity and good to excellent yields is reported. The procedure is mild, base-free, and operationally straightforward.
Synthesis of chiral 4-hydroxy-2,3-unsaturated carbonyl compounds from 3,4-epoxy alcohols by oxidation: Application in the formal synthesis of macrosphelide A
Chakraborty, Tushar K.,Purkait, Subhas,Das, Sanjib
, p. 9127 - 9135 (2007/10/03)
An interesting transformation during the oxidation of 3,4-epoxy alcohols 1a-d, derived from the corresponding homoallylic alcohols, led to the formation of 4-hydroxy-2,3-unsaturated carbonyls 2a-d in very good yields. One of these products 2c was transfor
[3+3] Annulation by sequential two electron and one electron allylation
Ward, Dale E.,Kaller, Brian F.
, p. 843 - 846 (2007/10/02)
3-phenylthio-2-(trimethylsilymethyl)propene is a convenient conjunctive reagent for the preparation of methylenecyclohexanes via a [3+3] annulation. The trimethylsilyl group facilitates the Lewis acid catalyzed allylation of an aldehyde or acetal while the phenylthio group directs a 6-endo-trig radical cyclization reaction.
