Structure–sweetness relationships for fructose analogs. Part III. 3-Deoxy-<scp>D</scp>-<i>erythro</i>-hexulose (3-deoxy-<scp>D</scp>-fructose): composition in solution and evaluation of sweetness

Szarek, Walter A.; Rafka, Robert J.; Yang, Te‐Fang; Martin, Olivier R.

doi:10.1139/v95-203

Cited by 15 publications

(10 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Spectroscopical data agree with published data [33] Supporting Information (see also the footnote on the first page of this article): 1 H-and 13 C-NMR spectra of compound 6a-d.…”

Section: -Deoxy-d-erythro-2-hexulose (6e)supporting

confidence: 85%

“…Following our route developed we were able to synthesize a variety of bioactive 3-deoxy-2-uloses ( www.eurjoc.orgoxyketoses 6a-e were accessible starting with N-acetyl--mannosamine (leading to 6a [30] ), -mannose (leading to 6b), -arabinose (leading to 6c), -erythrose (leading to 6d [16] ) and O-isopropylidene--glyceraldehyde (leading to 6e [33] ) as starting material in the initial chain-elongation reaction.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Permanganate Oxidation Revisited: Synthesis of 3‐Deoxy‐2‐uloses via Indium‐Mediated Chain Elongation of Carbohydrates

2010

View full text Add to dashboard Cite

Application of the Barbier‐type indium‐mediated allylation method to suitable substrates offers access to carbohydrates bearing a terminal olefin moiety. The C–C bond forming reaction generates a defined stereochemistry of the new chiral center and tolerates a wide variety of starting aldehydes thus allowing modifications in the carbohydrate backbone. Further transformations of the alkene moiety via an environmentally benign and subtle controlled protocol using potassium permanganate gives rise to the structural motif of 3‐deoxy‐2‐uloses in good yields. The final part of the reaction sequence focuses on the deprotection of the acetyl groups essential for the success of the oxidation step. The acidic and labile 3‐deoxy position of the target molecule is prone to elimination applying standard deacetylation conditions and therefore demands derivatisation of the molecule. The introduction of a thioketal moiety using microwave conditions shows promising results and subsequent standard transformations are applicable leading to the desired products.

show abstract

“…Spectroscopical data agree with published data [33] Supporting Information (see also the footnote on the first page of this article): 1 H-and 13 C-NMR spectra of compound 6a-d.…”

Section: -Deoxy-d-erythro-2-hexulose (6e)supporting

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Permanganate Oxidation Revisited: Synthesis of 3‐Deoxy‐2‐uloses via Indium‐Mediated Chain Elongation of Carbohydrates

2010

View full text Add to dashboard Cite

show abstract

“…To our knowledge, 3-deoxy-Dfructose is not available from natural sources, only a few reports can be found for the synthesis of 3-deoxyhexose, such as 3-deoxy-D-fructose. 10,11) So, the structures of two com- pounds will enrich the structural diversity of nature product. In addition, from a biosynthetic pathway perspective, it was possible that pollenopyrrosides A and B were formed by a series of reaction of 3-deoxy-D-fructose and 5-oxymethy1-2-formyl-pyrrole as showed in Chart 1.…”

Section: Restults and Discussionmentioning

confidence: 99%

Pollenopyrroside A and B, Novel Pyrrole Ketohexoside Derivatives from Bee-Collected Brassica campestris Pollen

et al. 2010

View full text Add to dashboard Cite

NoteBee-collected pollen is a hive product that bees pack pollen grains from the flower into pollen pellets on their hind legs with the help of combs and hairs, to feed their larvae in the early stages of development. The constituents of pollen are different according to the floral species or cultivars, 1) while flavonols are commonly encountered in the pollen of flowering plants and perform an essential physiological function in pollen germination and pollen tube growth. Brassica campestris L., also called rape, belongs to Brassica genus (Crucifer) and is widely grown in south of China as an economic crop. Bee-collected Brassica campestris pollen is often used in China as a healthy food and an herbal medicine in strengthening the body's resistance against disease. It has already been found to possess a wide range of biological activities, including antioxidant, 2) antitumor, 3) regulating serum lipids, 4) and treatment of prostatitis. 5) Up to date, bee-collected Brassica campestris pollen are known as a rich source of protein, polysaccharide, fatty acid and flavonoids.6) In our study on the active components of bee-collected Brassica campestris pollen, two novel pyrrole ketohexoside derivatives, named pollenopyrroside A (1) and pollenopyrroside B (2), were isolated from it. Their structures were identified on basis of spectroscopic data (UV, IR, MS, NMR and X-ray) and chemical evidence. Compounds 1 and 2 are two novel pyrrole ketohexoside derivatives with five-six and six-six member dioxaspirocycle, respectively (Fig. 1). Their cytotoxicities were evaluated against A549, Bel7420, BGC-823, HCT-8, and A2780. Restults and DiscussionCompound 1 7) These were supported by heteronuclear multiple bond connectivity (HMBC) correlations (Fig. 2) of H-7 with C-2 and C-3, of H-6 with C-4 and C-5, of H-3 with C-2, C-4, and C-5, and of H-4 with C-5 and C-2. In addition, the 1 Hand 13 C-NMR spectra showed the resonances of two methylene carbons at d C 52. 3.76 (1H, dd, Jϭ10.5, 10.5), 3.53 (1H, m)], one quaternary carbon at d C 95.0. These NMR data suggested that a deoxyketohexose moiety existed in 1. The connectivity of aglycone and sugar moiety was established on the basis of HMBC experiment. In the HMBC spectrum (Fig. 2), correlations of H-1Ј with C-5 and C-2Ј, and H-6 protons resonating at d H 4.93 (1H, d, Jϭ16.0 Hz) and 4.86 (1H, d, Jϭ16.0 Hz) with the quaternary carbon C-2Ј were observed. This quaternary carbon was also correlated with some protons of sugar. The above evidence confirmed that the deoxyketohexose moiety fused to the 5-oxymethy1-2-formyl-pyrrole fragment through oxygen and nitrogen atoms and an oxazine ring was formed. The addi- 983-985 (2010)

show abstract

“…31 For our purpose, a coupled enzymatic synthesis was clearly unattractive as neither this NADPH-dependent reductase nor its substrate was readily available. From the several reported chemical methods for 3dFru synthesis, 17,18,32,33 the Barton-McCombie deoxygenation protocol 34 starting from 1,2:4,5-di-O-isopropylidene-b-D-fructopyranose 35 followed by acid catalyzed acetal deprotection is the most straightforward. 17,32 In practice, attempted hexokinase catalyzed phosphorylation of synthetic 3dFru (Scheme 4) proceeded extremely sluggishly.…”

Section: Synthesis Of 3-deoxy-d-fructose 6-phosphatementioning

confidence: 99%

“…From the several reported chemical methods for 3dFru synthesis, 17,18,32,33 the Barton-McCombie deoxygenation protocol 34 starting from 1,2:4,5-di-O-isopropylidene-b-D-fructopyranose 35 followed by acid catalyzed acetal deprotection is the most straightforward. 17,32 In practice, attempted hexokinase catalyzed phosphorylation of synthetic 3dFru (Scheme 4) proceeded extremely sluggishly. 17 Although reactions were run at high (41 M) substrate concentration to compensate for the reported K M value of 750 mM for 3dFru with yeast hexokinase, and for its alleged reduced 24% relative rate with respect to natural fructose, 17 faint formation of a phosphorylated product required several days even with very high enzyme loadings.…”

Section: Synthesis Of 3-deoxy-d-fructose 6-phosphatementioning

confidence: 99%

Multi-enzymatic cascade synthesis of d-fructose 6-phosphate and deoxy analogs as substrates for high-throughput aldolase screening

Fessner¹,

Heyl²,

Rale³

2012

Catal. Sci. Technol.

View full text Add to dashboard Cite

We have evaluated different strategies for the one-pot synthesis of D-fructose 6-phosphate and its 1-deoxy and 3-deoxy analogs from readily available starting materials, by building up ''artificial metabolisms'' in vitro. The first consisted of an aldol cleavage-aldol formation cascade, in which glyceraldehyde 3-phosphate as the central intermediate is generated from fructose 1,6-bisphosphate and consumed in situ for a consecutive carboligation step catalyzed by fructose 6-phosphate aldolase (FSA). The second approach consisted of an aldolase-kinase coupling, in which the unphosphorylated ketose was produced in situ by FSA-catalyzed carboligation, followed by a hexokinase-catalyzed phosphorylation step. While both approaches profited from the high stereoselectivity and stability of the aldolases used, the first approach proved to be the most practical, effective and economical, whereas the second strongly depends on the substrate specificity of hexokinase, which shows inferior catalytic efficiency with the 1-deoxy substrate. Phosphorylation of 3-deoxyfructose failed because, contradictory to a literature report, this compound was found not to be acceptable as a substrate of yeast hexokinase.

show abstract

Structure–sweetness relationships for fructose analogs. Part III. 3-Deoxy-D-erythro-hexulose (3-deoxy-D-fructose): composition in solution and evaluation of sweetness

Cited by 15 publications

References 27 publications

Permanganate Oxidation Revisited: Synthesis of 3‐Deoxy‐2‐uloses via Indium‐Mediated Chain Elongation of Carbohydrates

Permanganate Oxidation Revisited: Synthesis of 3‐Deoxy‐2‐uloses via Indium‐Mediated Chain Elongation of Carbohydrates

Pollenopyrroside A and B, Novel Pyrrole Ketohexoside Derivatives from Bee-Collected Brassica campestris Pollen

Multi-enzymatic cascade synthesis of d-fructose 6-phosphate and deoxy analogs as substrates for high-throughput aldolase screening

Contact Info

Product

Resources

About