95639-53-5

Upstream product

• 81308-73-8 (3R,5R)-3,4,5-Tris-benzyloxy-cyclohexanone 
• 189758-77-8 methyl 3,4-di-O-benzyl-2-deoxy-5-methylene-α-D-xylopyranoside 
• 13145-22-7 methyl 2-deoxy-α-D-glucopyranoside 
• 506423-07-0 (1R,2R,3R,5S)-2,3-Bis-benzyloxy-5-(tert-butyl-dimethyl-silanyloxy)-cyclohexanol 
• 506423-05-8 (2S,3R,5R)-2,3-Bis-benzyloxy-5-(tert-butyl-dimethyl-silanyloxy)-cyclohexanone 
• 506423-10-5 (3R,5R)-3,4,5-Tris-benzyloxy-cyclohexanol 
• 6752-48-3 methyl 4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 
• 725268-38-2 (2S,3R)-2,3-Bis-benzyloxy-5-hydroxy-cyclohexanone 
• 175844-98-1 methyl 3,4-di-O-benzyl-2,6-dideoxy-6-iodo-α-D-glucopyranoside 
• 119943-96-3 Methyl 3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-arabino-hexopyranoside 
• 145149-85-5 Methyl 3,4-di-O-benzyl-2-deoxy-α-D-arabino-hexopyranoside 
• 6087-40-7 (2R,3S,4R,6S)-3,4-diacetoxy-2-(acetoxymethyl)-6-methoxytetrahydro-2H-pyran 
• 77-95-2 D-(-)-quinic acid 

Downstream Products

• 141404-08-2 (3R,5R)-3,5-bis[tert-butyl(dimethyl)silyloxy]-4-hydroxycyclohexanone 
• 150-76-5 4-methoxy-phenol 
• 123-31-9 hydroquinone 
• 1965-09-9 4,4'-dihydroxydiphenyl ether 

Relevant academic research and scientific papers

Degradation of unprotected aldohexonic acids to aldopentoses promoted by light and oxygen

Herein reported is a photoredox-catalyzed oxidative degradation reaction of unprotected aldohexonic acids, which are shortened by one-carbon to the corresponding aldopentoses. Oxygen including aerial oxygen is used as a terminal oxidant. The mild reaction conditions permit even disaccharides to successfully undergo the degradation reaction with the glycosidic bond remaining intact. Quinic acid is also converted to a useful chiral synthetic intermediate.

Biomass-Based and Oxidant-Free Preparation of Hydroquinone from Quinic Acid

A biomass-based route to the preparation of hydroquinone starting from the renewable starting material quinic acid is described. Amberlyst-15 in the dry form promoted the one-step formation of hydroquinone from quinic acid in toluene without any oxidants or metal catalysts in 72 % yield. Several acidic polymer-based resins and organic acids as promoters as well as a variety of reaction conditions were screened including temperature, concentration and low- and high-boiling-point solvents. A 1:4 (w/w) ratio of quinic acid/Amberlyst-15 was determined to be optimal to promote hydroquinone formation with only traces of a dimeric side-product. A mechanism has been proposed based on the decarbonylation of protonated quino-1,5-lactone that is supported by experimental and computational calculation data.

Synthesis of a-ring synthon of 19-nor-1alpha,25-dihydroxyvitamin D3 from (D)-glucose

The present invention provides a method for the synthesis of an A-ring synthon phosphine oxide used in the preparation of 19-nor vitamin D compounds, and to novel synthetic intermediates formed during the synthesis. The new method prepares the phosphine oxide from (D)-glucose.

Novel synthesis of 2-substituted 19-norvitamin D A-ring phosphine oxide from D-glucose as a building block

19-Norvitamin D A-ring phosphine oxide 5 was synthesized by a new sequence mode starting from D-glucose as a chiral template. Transformation of the pyranoside ring into the A-ring carbocycle was achieved by the Pd-catalyzed Ferrier rearrangement. The phosphine oxide 5 was obtained in an 18% overall yield by this novel cost-effective method.

Benzene-free synthesis of hydroquinone

All current routes for the synthesis of hydroquinone utilize benzene as the starting material. An alternate route to hydroquinone has now been elaborated from glucose. While benzene is a volatile carcinogen derived from nonrenewable fossil fuel feedstocks, glucose is nonvolatile, nontoxic, and derived from renewable plant polysacharrides. Glucose is first converted into quinic acid using microbial catalysis. Quinic acid is then chemically converted into hydroquinone. Under fermentor-controlled conditions, Escherichia coli QP1.1/pKD12.138 synthesizes 49 g/L of quinic acid from glucose in 20% (mol/mol) yield. Oxidative decarboxylation of quinic acid in clarified, decolorized, ammonium ion-free fermentation broth with NaOCl and subsequent dehydration of the intermediate 3(R),5(R)-trihydroxycyclohexanone afforded purified hydroquinone in 87% yield. Halide-free, oxidative decarboxylation of quinic acid in fermentation broth with stoichiometric quantities of (NH4)2Ce(SO4)3 and V2O5 afforded hydroquinone in 91% and 85% yield, respectively. Conditions suitable for oxidative decarboxylation of quinic acid with catalytic amounts of metal oxidant were also identified. Ag3PO4 at 2 mol % relative to quinic acid in fermentation broth catalyzed the formation of hydroquinone in 74% yield with K2S2O8 serving as the cooxidant. Beyond establishing a fundamentally new route to an important chemical building block, oxidation of microbe-synthesized quinic acid provides an example of how the toxicity of aromatics toward microbes can be circumvented by interfacing chemical catalysis with biocatalysis.