69351-19-5

Upstream product

• 57-48-7 D-Fructose 
• 77-76-9 2,2-dimethoxy-propane 
• 15080-25-8 C₁₂H₂₀O₆ 
• 7660-25-5 D-fructose 
• 6347-01-9 fructopyranose 
• 20880-92-6 2,3;4,5-di-O-isopropylidene-β-D-fructopyranose 
• 25018-67-1 1,2;4,5-di-O-isopropylidene-β-D-(-)-fructopyranose 

Downstream Products

• 108680-92-8 1,2:4,5-di-O-isopropylidene-3-C-phenyl-β-D-fructopyranose 
• 18422-54-3 1,2;4,5-di-O-isopropylidene-β-D-fructopyranose 
• 187236-00-6 C₂₃H₃₀O₆ 
• 439828-63-4 (5S,8R,9R)-2,2-dimethyl-10-oxo-1,3,6-trioxaspiro[4,5]decane-8,9-diyl diacetate 
• 532394-78-8 3-O-benzoyl-3-C-cyano-1,2:4,5-di-O-isopropylidene-β-D-psicopyranose 
• 532394-80-2 1,2:4,5-di-O-isopropylidene-3-C-(5-phenyl-1,2,4-oxadiazol-3-yl)-β-D-psicopyranose 
• 532394-79-9 3-O-benzoyl-3-C-(N-hydroxycarbamimidoyl)-1,2:4,5-di-O-isopropylidene-β-D-psicopyranose 
• 187236-13-1 (5S,8R,9R,10R)-9-Methoxy-2,2-dimethyl-10-(5-phenyl-pentyl)-1,3,6-trioxa-spiro[4.5]decane-8,10-diol 

Relevant academic research and scientific papers

Studies on asymmetric total synthesis of (?)-β-hydrastineviaa chiral epoxide ring-opening cascade cyclization strategy

Herein, facile and enantioselective approaches to synthesize the core phthalide tetrahydroisoquinoline scaffold of (?)-β-hydrastineviaboth a CF3COOH-catalyzed (86% ee) and KHMDS-catalyzed (78% ee) epoxide ring-opening/transesterification cascade cyclization from chiral epoxide under very mild conditions are described. The key elements include a highly enantioselective epoxidation using the Shi ketone catalyst and an intramolecular CF3COOH-catalyzed cascade cyclization in one pot, and a late-stage C-3′ epimerization under MeOK/MeOH conditions as the key steps to achieve the first total synthesis of (?)-β-hydrastine (up to 81% ee).

IMPROVED SYNTHESIS OF AN EPOXIDATION-CATALYST

The present invention relates to an improved process to produce a specific and very efficient epoxidation-catalyst (1,2:4,5-Di-O-isopropylidene-β-D-erythro-2,3-hexodiulo-2,6-pyranose).

Safe and Scalable Aerobic Oxidation by 2-Azaadamantan-2-ol (AZADOL)/NOx Catalysis: Large-Scale Preparation of Shi's Catalyst

A method for safe and scalable aerobic alcohol oxidation using 2-azaadamantan-2-ol (AZADOL), an azaadamantane-type hydroxylamine catalyst, with a NOx cocatalyst in a conventional batch reactor has been developed. The use of 2 mol % AZADOL and 10 mol % NaNO2 was determined to promote aerobic alcohol oxidation quantitatively within a reasonable time (8 h). Safety is ensured by controlling the reaction temperature below the flash point of the acetic acid solvent. The robustness of the developed method is demonstrated by the 500 g scale oxidation of diacetone fructose into Shi's catalyst for asymmetric epoxidation.

An alkoxyamine compound, alkoxy alcohol oxidation catalyst and method of using the alcohol oxidation

PROBLEM TO BE SOLVED: To provide a novel alkoxyamine compound which can be easily manufactured and applied suitably as an alcohol oxidation catalyst capable of exerting sufficiently high catalytic activity in oxidation of primary and secondary alcohols.SOLUTION: There is provided an alkoxyamine compound with a homoadamantane skeleton represented by the general formula (1) in the figure. [In the formula (1), Rand Rare each independently any one selected from the group consisting of a hydrogen atom and alkyl groups that may be substituted.

Synthesis method of fructose-derived chiral ketone catalyst

The invention provides a synthesis method of a fructose-derived chiral ketone catalyst. The method comprises the following steps: (1) by using D-fructose and acetone as a raw material, carrying out ketonization reaction at 10-45 DEG C by using concentrated sulfuric acid as a catalyst to obtain a first intermediate; (2) dissolving the first intermediate in an organic solvent, adding molecular sieve powder, and carrying out oxidation at 50-80 DEG C by using PCC as an oxidant, thereby obtaining a second intermediate; (3) carrying out hydrolysis on the second intermediate at 10-45 DEG C under the actions of acetic acid, water and zinc chloride, thereby obtaining a third intermediate; after the hydrolysis finishes, adding acetic anhydride, and carrying out esterification reaction to obtain a fructose-derived chiral ketone hydrate; and (4) eliminating water molecules in the fructose-derived chiral ketone hydrate by using a polar organic solvent, thereby obtaining the fructose-derived chiral ketone. The method has the advantages of simple technique, low raw material cost and mild reaction conditions, is convenient for separation and purification, can be used for quickly and efficiently synthesizing the fructose-derived chiral ketone catalyst, and is more suitable for industrial production.

Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: Optimum catalyst combinations and their substrate scope

The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts.

Efficient magnetic and recyclable SBILC (supported basic ionic liquid catalyst)-based heterogeneous organocatalysts for the asymmetric epoxidation of trans-methylcinnamate

A green alternative, based on the use of an efficient and recyclable chiral ketone@SBILC@MWCNT@Fe3O4 catalytic system (Y = 35%, S = 100% and ee = 100%), was developed for the asymmetric epoxidation of trans-methylcinnamate to (2R,3S)

Stable TEMPO and ABNO Catalyst Solutions for User-Friendly (bpy)Cu/Nitroxyl-Catalyzed Aerobic Alcohol Oxidation

Two solutions, one consisting of bpy/TEMPO/NMI and the other bpy/ABNO/NMI (bpy =2,2′-bipyridyl; TEMPO = 2,2,6,6-tetramethylpiperidine N-oxyl, ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl; NMI = N-methylimidazole), in acetonitrile are shown to have good long-term stability (≥1 year) under air at 5 °C. The solutions may be combined in appropriate quantities with commercially available [Cu(MeCN)4]OTf to provide a convenient catalyst system for the aerobic oxidation of primary and secondary alcohols.

Mechanistic insight into aerobic alcohol oxidation using NOx-nitroxide catalysis based on catalyst structure-activity relationships

The mechanism of an NOx-assisted, nitroxide(nitroxyl radical)-catalyzed aerobic oxidation of alcohols was investigated using a set of sterically and electronically modified nitroxides (i.e., TEMPO, AZADO (1), 5-F-AZADO (2), 5,7-DiF-AZADO (3), 5-MeO-AZADO (4), 5,7-DiMeO-AZADO (5), oxa-AZADO (6), TsN-AZADO (7), and DiAZADO (8)). The motivation for the present study stemmed from our previous observation that the introduction of an F atom at a remote position from the nitroxyl radical moiety on the azaadamantane nucleus effectively enhanced the catalytic activity under typical NOx-mediated aerobic-oxidation conditions. The kinetic profiles of the azaadamantane-N-oxyl-[AZADO (1)-, 5-F-AZADO (2)-, and 5,7-DiF-AZADO (3)]-catalyzed aerobic oxidations were closely investigated, revealing that AZADO (1) showed a high initial reaction rate compared to 5-F-AZADO (2) and 5,7-DiF-AZADO (3); however, AZADO-catalyzed oxidation exhibited a marked slowdown, resulting in ～90% conversion, whereas 5-F-AZADO-catalyzed oxidation smoothly reached completion without a marked slowdown. The reasons for the marked slowdown and the role of the fluoro group are discussed. Oxa-AZADO (6), TsN-AZADO (7), and DiAZADO (8) were designed and synthesized to confirm their comparable catalytic efficiency to that of 5-F-AZADO (2), providing supporting evidence for the electronic effect on the catalytic efficiency of the heteroatoms under NOx-assisted aerobic-oxidation conditions.

Concise stereoselective total synthesis of (+)-muricatacin and (+)-epi-muricatacin

Efficient stereoselective total synthesis of (+)-muricatacin (1) and (+)-epi-muricatacin (8) was accomplished from commercially available chemical pent-4-ynoic acid via Shi's asymmetric epoxidation and Mitsunobu reaction as the key steps in 17.8% and 26.9