5792-35-8Relevant articles and documents
Base-Mediated Cascade Aldol Addition and Fragmentation Reactions of Dihydroxyfumaric Acid and Aromatic Aldehydes: Controlling Chemodivergence via Choice of Base, Solvent, and Substituents
Ward, George,Liotta, Charles L.,Krishnamurthy, Ramanarayanan,France, Stefan
supporting information, p. 14219 - 14233 (2018/10/24)
The diester derivative of dihydroxyfumaric acid (DHF) has been used exclusively as an electrophile in organic synthesis. However, the synthetic utility of DHF's nucleophilic reactivity, contained in the ene-diol moiety, has been underexplored. Inspired by recently observed pH-dependent chemodivergent nucleophilic aldol reactions of dihydroxyfumarate (DHF2-) with glyoxylate and formaldehyde, we report herein the control and synthetic application of base-controlled chemodivergent reactions between dihydroxyfumarate and aromatic and heteroaromatic aldehydes. With hydroxide as the base in a predominantly aqueous medium, aldol addition followed by deoxalation occurs to provide various 3-aryl-2,3-dihydroxypropanoic acids. With triethylamine as the base in THF, 1-aryl-2,3-dihydroxypropanones are the products of the reaction. In order to understand the difference in reactivity between DHF, its dicarboxylate, and its dimethyl ester, we undertook computational and experimental studies that provide a rationale as to why the dihydroxyfumarate (DHF2-) is a nucleophile while the corresponding diester reacts as an electrophile.
Stereoselectivity of an ω-transaminase-mediated amination of 1,3-dihydroxy-1-phenylpropane-2-one
Smithies, Kirsty,Smith, Mark E.B.,Kaulmann, Ursula,Galman, James L.,Ward, John M.,Hailes, Helen C.
body text, p. 570 - 574 (2009/09/05)
The stereoselectivity of a recently isolated ω-transaminase from Chromobacterium violaceum in the amination of 1,3-dihydroxy-1-phenylpropan-2-one has been determined. The enzyme is not enantioselective towards a racemic mixture of 1,3-dihydroxy-1-phenylpr
The Enhancement of Formose Formation with 2-Hydroxyacetophenone. A mechanism Involving Aldol and Retro-aldol Reactions
Sakai, Tomoya,Ishizaki, Masahiko,Goto, Masafumi
, p. 2409 - 2414 (2007/10/02)
The rapid aldol addition of formaldehyde to 2-hydroxyacetophenone (HAP), an efficient accelerator for formose formation, took place to yield addition products of HAP with one and two molecules of formaldehyde at 35 deg C in an aqueous 40percent methanol mixture of formaldehyde, HAP, and Ca(OH)2.No further addition product with more than two molecules of formaldehyde attached to HAP was detected throughout the reaction.On the contrary, benzaldehyde and benzoic acid were formed, accompanied by formose sugars.The initial molar amount of HAP corresponded to the sum of the compounds substituted with the phenyl group including benzaldehyde and benzoic acid.The retro-aldol reaction of the HAP derivatives is likely to be involved in the overall reaction to yield glycolaldehyde or trioses, which are good accelerators for formose formation.
