A Dodecitol from the Alkaline Electroreduction of D-Glucose^1,2

Electrosynthesis of Biobased Chemicals Using Carbohydrates as a Feedstock

“…d,l-glucitol [96] and a dodecitol [97] were also detected. The formation of dodecitol was assumed to arise from the electroreduction of the aldehyde group of two glucose molecules.…”

“…However, a range of undesired by-products were also present, depending on the reaction conditions. Wolfrom et al documented a very thorough study to characterise the various products present after the electro-reduction of glucose on a Hg cathode [ 93 , 94 , 95 , 96 , 97 ]. From the commercial sorbitol ( 41 ) in weakly alkaline medium (pH = 7–10) and at a temperature below 30 °C, d -mannitol (1% yield), and 2-deoxysorbitol ( 43 , 5% yield) could be isolated.…”

“…As expected, sorbitol ( 41 ) and mannitol ( 42 ) were isolated, as well as 2-deoxysorbitol ( 43 ) and 1-deoxymannitol ( 44 ). d , l -glucitol [ 96 ] and a dodecitol [ 97 ] were also detected. The formation of dodecitol was assumed to arise from the electroreduction of the aldehyde group of two glucose molecules.…”

Electrochemical Coupling of Biomass‐Derived Acids: New C8 Platforms for Renewable Polymers and Fuels

“…Looking to the literature, there has been little activity around the direct coupling of sugars, although it was interesting to find that glucose itself has been madet ou ndergo ac athodic process whereby it wastransformed into ad odecitol, presumably via its aldehyde form. [3] The electrolysis however of sugar derivativesp resents av iable alternative, and we were drawn to reports of the dimerizationo fl evulinic acid (1)t o2 ,7-octanedione (2)( Scheme 2). [4][5][6] The recent upsurge of interesti n1 as ar enewable, carbohydrate-derived platform molecule, and the continuing development of technologiest op roduce it on an industrial scale, [7] advance dione 2 as ap otential "secondgeneration"p latform only two steps removed from biomass.…”

From Higher Carbon Sugars to Carbocyclic Sugar Mimics

“…Only very limited examples of such derivatives could be found in the literature. The first example of a C-C-linked disaccharide, a dodecitol (by-product of electroreduction of D-glucose), was described in 1951 by Wolfrom [7]. In 1969, Ferrier and Prasad [8] reported a "dimer" obtained from 3,4,6-tri-O-acetyl-D-glucal, and in 1971 Roy and Chilton [9] synthesized a diastereoisomeric mixture of hexadecitols from 2,3:5,6-di-O-isopropylidene-Dmannose and acetylene.…”