5-Hydroxymethyl-2 -furanone, reaction

The reaction between the chiral furanones (/ )-/3-angelica lactone 129 (Z = H) and 5-hydroxymethyl-2(5//)-furanone 143 (Z = OH) with cyclopentadiene was... 

Thermolysis of D-fructose in acid solution provides 11 and 2-(2-hydrox-yacetyl)furan (44) as major products. Earlier work had established the presence of 44 in the product mixtures obtained after acid-catalyzed dehydrations of D-glucose and sucrose. Eleven other products were identified in the D-fructose reaction-mixture, including formic acid, acetic acid, 2-furaldehyde, levulinic acid, 2-acetyl-3-hydroxyfuran (isomaltol), and 4-hydroxy-2-(hydroxymethyl)-5-methyl-3(2//)-furanone (59). Acetic acid and formic acid can be formed by an acid-catalyzed decomposition of 2-acetyl-3-hydroxyfuran, whereas levulinic acid is a degradation prod-uct of 11. 2,3-Dihydro-3,5-dihydroxy-6-methyl-4//-pyran-4-one has also been isolated after acid treatment of D-fructose.The pyranone is a dehydration product of the pyranose form of l-deoxy-D-eo f o-2,3-hexodiulose. In aqueous acid seems to be the major reaction product of the pyranone. 

Preparative Methods both enantiomers of dihydro-5-(hydroxymethyl)-2(3H) furanone and their trityl derivatives are commercially available but expensive. The simplest and by far most popular method for preparing (5)-dihydro-5-(hydroxymethyl)-2(3H)-furanone (2) consists of enantiospecific deamination of L-glutamic acid and subsequent selective reduction of the resulting carboxylic acid (13) (eq 1). Purification of the intermediate acid (13) by crystallization and not by distillation is recommended in order to secure an excellent optical yield (>98% ee). Likewise, (f )-dihydro-5-(hydroxymethyl)-2(3//)-furanone (1) (>98% ee) can be obtained from o-glutamic acid. As the latter is considerably more expensive than its natural antipode, an appealing option is to convert the (5)-lactone into its enantiomer (eq 2)P Also available and equally useful is an inversion route to (f )-dihydro-5-(trityloxymethyl)-2(3H)-furanone (5) by way of the Mitsunobu reaction (eq 3). ... 

These can be tentatively assigned from mechanistic projections, based on thermal generation studies (2) and assignment to the molecular ion as butan-2,3-dione (ion 87, diacetyl), 1-hydroxy butan-2,3-dione (ion 103), 4-hydroxy pentan-2,3-dione (ion 117), (5-hydroxymethyl) furfural (ion 127), y-pyranone or 4-furanone (ion 145), deoxyosone (ion 163). In comparison when the reaction is conducted in the presence of leucine (Ipil/min water) the primary ions formed are ion 74, 88,142, and 156 (Figure 3). 

Perhaps the most simple reaction is the direct opening of the heterocycle either through acidic hydrolysis or oxidative opening to produce saturated or unsaturated 1,4-dicarbonyl derivatives 11 and 12 respectively. Reduction and oxidation of the furan nucleus without ring-opening are also facile methods for de-aromatization. Oxidation can provide direct access to both 2- and 3-furanones (13-14), hydropyrones 15 (when a hydroxymethyl group is placed in the 2-position), or maleic anhydrides 16. Likewise, partial reduction can lead to 2,3- or 3,4-dihydrofurans (17-18) while full reduction of the heterocycle produces the tetrahydrofiiran system 19. These... 

Hiebl, J. Ledl, F. Severin, T. Isolation of 4-hydroxy-2-(hydroxymethyl) - 5-methyl-3(2H)- furanone from sugar amino acid reaction mixtures. J. Agric. Food Chem. 1987, 35, 990-993. 

S)-5-Hydroxymethyl-2(5H)-furanone (8), derived from D-ribono-lactone, was used as an intermediate in a synthesis of the 6a-carbocycline analogue (9), with a Pauson-Khand reaction being used to build up the ring system from enyne (10) (Scheme 4). When alcohol (8) underwent Diels-Alder reaction with cyclopentadiene, either the (2S, 3R)-isomer (11) or its enantiomer could be produced by appropriate manipulation of the initial adduct face-selective Lewis-acid-catalysed Diels-Alder reactions of a,iS-unsaturated esters derived from D-mannitol could be used to produce the (R,R)-isomer (12) or its enantiomer.This chemistry was extended to give syntheses of (+)-0-santalene (13) and its enantiomer from (8) the starting material was prepared as described in Vol. 20 p.260, but a number of other papers dealing with routes to this intermediate are mentioned in the next section. 

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