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Efficient and Selective Cu/Nitroxyl-Catalyzed Methods for Aerobic Oxidative Lactonization of Diols

Cu/nitroxyl catalysts have been identified that promote highly efficient and selective aerobic oxidative lactonization of diols under mild reaction conditions using ambient air as the oxidant. The chemo- and regioselectivity of the reaction may be tuned by changing the identity of the nitroxyl cocatalyst. A Cu/ABNO catalyst system (ABNO = 9-azabicyclo[3.3.1]nonan-N-oxyl) shows excellent reactivity with symmetrical diols and hindered unsymmetrical diols, whereas a Cu/TEMPO catalyst system (TEMPO = 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl) displays excellent chemo- and regioselectivity for the oxidation of less hindered unsymmetrical diols. These catalyst systems are compatible with all classes of alcohols (benzylic, allylic, aliphatic), mediate efficient lactonization of 1,4-, 1,5-, and some 1,6-diols, and tolerate diverse functional groups, including alkenes, heterocycles, and other heteroatom-containing groups.

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Reference£º
Tetrahydrofuran – Wikipedia,
Tetrahydrofuran | (CH2)3CH2O – PubChem

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Enantioselective synthesis of 2-isocephem and 2-isooxacephem antibiotics

The azido lactone 8 was prepared in a highly stereoselective manner by introduction of an azide function to the lactone 6 derived from L-aspartic acid, and then was converted into (2S,3S)-3-amino-2-azido-4-hydroxybutanoic acid 4. Four-component condensation of the amino acid 4, p-nitrobenzyl isocyanide and formaldehyde or 2,2-diethoxyacetaldehyde furnished the corresponding 3,4-cis-azetidinone 16 or 26 in excellent yield. 3-Methoxy-2-isooxacephalosporin was prepared by the intramolecular acylation of imidazolide 23 derived from compound 16. 3-Unsubstituted 2-isocephem and 2-isooxacephem analogues were prepared from the azetidinone 26.

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. HPLC of Formula: C9H15NO4, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 104227-71-6, in my other articles.

Reference£º
Tetrahydrofuran – Wikipedia,
Tetrahydrofuran | (CH2)3CH2O – PubChem

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Diamine derivatives

A compound represented by the general formula (1): Q1-Q2-T0-N(R1)-Q3-N(R2)-T1-Q4??(1) wherein R1 and R2 are hydrogen atoms or the like; Q1 is a saturated or unsaturated, 5- or 6-membered cyclic hydrocarbon group which may be substituted, or the like; Q2 is a single bond or the like; Q3 is a group 1 in which Q5 is an alkylene group having 1 to 8 carbon atoms, or the like; and T0 and T1 are carbonyl groups or the like; a salt thereof, a solvate thereof, or an N-oxide thereof. The compound is useful as an agent for preventing and/or treating cerebral infarction, cerebral embolism, myocardial infarction, angina pectoris, pulmonary infarction, pulmonary embolism, Buerger’s disease, deep venous thrombosis, disseminated intravascular coagulation syndrome, thrombus formation after valve or joint replacement, thrombus formation and reocclusion after angioplasty, systemic inflammatory response syndrome (SIRS), multiple organ dysfunction syndrome (MODS), thrombus formation during extracorporeal circulation, or blood clotting upon blood drawing.

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Reference£º
Tetrahydrofuran – Wikipedia,
Tetrahydrofuran | (CH2)3CH2O – PubChem

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With the rapid development and complex challenges of chemical substances, new drug synthesis pathways are usually the most effective.104227-71-6,(S)-tert-Butyl (5-oxotetrahydrofuran-3-yl)carbamate,as a common compound, the synthetic route is as follows.

REFERENTIAL EXAMPLE 195 tert-Butyl (3S,4S)-4-azido-5-oxotetrahydro-3-furanylcarbamate: 1 M Lithium bis(trimethylsilyl)amide (tetrahydrofuran solution, 8.65 ml) was added dropwise to a solution of the compound (0.87 g) obtained in Referential Example 194 in tetrahydrofuran (20 ml) at -78 C., and the mixture was stirred for 30 minutes. After a solution of p-toluenesulfonylazide (1.02 g) in tetrahydrofuran (10 ml) was then added, and the mixture was stirred for 5 minutes, trimethylchlorosilane (1.7 ml) was added, and the mixture was stirred for 2 hours while the temperature of the system was gradually raised to room temperature. The reaction mixture was diluted with diethyl ether, washed with 10% hydrochloric acid, a 5% saturated aqueous solution of sodium hydrogencarbonate and saturated aqueous solution of sodium chloride, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The resultant residue was purified by column chromatagraphy on silica gel (hexane:ethyl acetate=4:1) to obtain the title compound (0.62 g). 1H-NMR (CDCl3) delta: 1.46(9H,s), 4.09(1H,dt,J=15.3, 7.6 Hz), 4.12-4.23(1H,m), 4.37-4.50(1H,m), 4.54(1H,dd,J=9.0, 7.6 Hz), 4.81-4.90(1H,m)

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Reference£º
Patent; DAIICHI PHARMACEUTICAL CO., LTD.; US2005/20645; (2005); A1;,
Tetrahydrofuran – Wikipedia
Tetrahydrofuran | (CH2)3CH2O – PubChem

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104227-71-6, (S)-tert-Butyl (5-oxotetrahydrofuran-3-yl)carbamate is a Tetrahydrofurans compound, ?involved in a variety of chemical synthesis. Rlated chemical reaction is continuously updated

4-Bromoaniline (172 mg) was dissolved in dichloromethane (5 ml). To the solution, trimethylaluminum (1.8 M solution in toluene, 0.556 ml) was added, and the mixture was stirred at room temperature for 15 minutes. Tert-butyl N-[(3S)-5-oxotetrahydrofuran-3-yl]carbamate (201 mg) was added to the reaction solution, and the mixture was stirred overnight at room temperature, then stirred at 60 C. for 1 hour, and then further heated to reflux for 1 hour. (0416) The same procedures as above were performed using 4-bromoaniline (2.56 g), and two lots were combined. Water was added to the reaction solution, followed by extraction from the aqueous layer with ethyl acetate. The aqueous layer was filtered through celite. After extraction from the filtrate with dichloromethane, these two organic layers were combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane-ethyl acetate) to obtain the title compound (3.82 g). (0417) 1H-NMR (DMSO-d6) delta: 1.34 (9H, s), 2.39 (1H, dd, J=14.9, 7.4 Hz), 2.54 (1H, dd, J=14.9, 5.7 Hz), 3.28-3.35 (1H, m), 3.36-3.41 (1H, m), 3.82-3.88 (1H, m), 4.70-4.78 (1H, m), 6.59 (1H, d, J=8.6 Hz), 7.45-7.48 (2H, m), 7.54-7.57 (2H, m), 9.97 (1H, s). (0418) ESI-MS (m/z): 373, 375 (M+H)+.

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Reference£º
Patent; Daiichi Sankyo Company, Limited; Takeda, Yasuyuki; Yoshikawa, Kenji; Kagoshima, Yoshiko; Yamamoto, Yuko; Tanaka, Ryoichi; Tominaga, Yuichi; Kiga, Masaki; Hamada, Yoshito; (132 pag.)US2016/46639; (2016); A1;,
Tetrahydrofuran – Wikipedia
Tetrahydrofuran | (CH2)3CH2O – PubChem

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4-Bromoaniline (172 mg) was dissolved in dichloromethane (5 ml). To the solution, trimethylaluminum (1.8 M solution in toluene, 0.556 ml) was added, and the mixture was stirred at room temperature for 15 minutes. Tert-butyl N-[(3S)-5-oxotetrahydrofuran-3-yl]carbamate (201 mg) was added to the reaction solution, and the mixture was stirred overnight at room temperature, then stirred at 60 C. for 1 hour, and then further heated to reflux for 1 hour. (0416) The same procedures as above were performed using 4-bromoaniline (2.56 g), and two lots were combined. Water was added to the reaction solution, followed by extraction from the aqueous layer with ethyl acetate. The aqueous layer was filtered through celite. After extraction from the filtrate with dichloromethane, these two organic layers were combined, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane-ethyl acetate) to obtain the title compound (3.82 g). (0417) 1H-NMR (DMSO-d6) delta: 1.34 (9H, s), 2.39 (1H, dd, J=14.9, 7.4 Hz), 2.54 (1H, dd, J=14.9, 5.7 Hz), 3.28-3.35 (1H, m), 3.36-3.41 (1H, m), 3.82-3.88 (1H, m), 4.70-4.78 (1H, m), 6.59 (1H, d, J=8.6 Hz), 7.45-7.48 (2H, m), 7.54-7.57 (2H, m), 9.97 (1H, s). (0418) ESI-MS (m/z): 373, 375 (M+H)+.

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Reference£º
Patent; Daiichi Sankyo Company, Limited; Takeda, Yasuyuki; Yoshikawa, Kenji; Kagoshima, Yoshiko; Yamamoto, Yuko; Tanaka, Ryoichi; Tominaga, Yuichi; Kiga, Masaki; Hamada, Yoshito; (132 pag.)US2016/46639; (2016); A1;,
Tetrahydrofuran – Wikipedia
Tetrahydrofuran | (CH2)3CH2O – PubChem

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With the rapid development and complex challenges of chemical substances, new drug synthesis pathways are usually the most effective.104227-71-6,(S)-tert-Butyl (5-oxotetrahydrofuran-3-yl)carbamate,as a common compound, the synthetic route is as follows.

To a solution of the compound obtained in Referential Example 194 (0.87 g) in tetrahydrofuran (20 mL) was added dropwise lithium bis(trimethylsilyl)amide (as 1M tetrahydrofuran solution, 8.65 mL) at -78C, and the thus-obtained mixture was stirred for 30 minutes. Subsequently, a solution of p-toluenesulfonyl azide (1.02 g) in tetrahydrofuran (10 mL) was added thereto, followed by stirring for 5 minutes, and after trimethylchlorosilane (1.7 mL) was added thereto, the thus-obtained mixture was gradually brought back to room temperature while being stirred. After the reaction mixture was stirred for 2 hours, the mixture was diluted with diethyl ether, and the diluted mixture was washed with 10% aqueous HCl, 5% saturated aqueous sodium hydrogencarbonate, and saturated brine, followed by drying over sodium sulfate anhydrate. The solvent was distilled away under reduced pressure, and the residue was purified by silica gel column chromatography (hexane : ethyl acetate = 4:1), to thereby give the title compound (0.62 g).1H-NMR(CDCl3) delta:1.46(9H, s), 4.09(1H, dt, J=15.3, 7.6Hz), 4.12-4.23(1H, m), 4.37-4.50(1H, m), 4.54(1H, dd, J=9.0, 7.6Hz), 4.81-4.90(1H, m).

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Reference£º
Patent; DAIICHI PHARMACEUTICAL CO., LTD.; EP1577301; (2005); A1;,
Tetrahydrofuran – Wikipedia
Tetrahydrofuran | (CH2)3CH2O – PubChem

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Step 1: At -10 C,Diisopropylamine (436 mg, 4.3 mmol) and n-butyllithium (2.5 M, 1.7 mL,A solution of 4.3 mmol) in tetrahydrofuran (1 mL) was stirred for 10 minutes and then the reaction was cooled to -70 C. A solution of (S)-(5-oxotetrahydrofuran-3-yl)carbamic acid tert-butyl ester (289 mg, 1.4 mmol) in tetrahydrofuran (1 mL) was slowly added dropwise to the above reaction system, and the obtained mixture was stirred for 30 minutes. A white solid is formed. Then, a solution of the compound Ia-5 (280 mg, 0.72 mmol) in tetrahydrofuran (1 mL) was slowly added dropwise to the above reaction system. The resulting mixture was stirred at -40 C for 30 minutes. The reaction system was quenched with saturated aqueous sodium hydrogen sulfate and extracted with EtOAc. Separating organic phase, there isThe machine phase is dried over anhydrous sodium sulfate, filtered and concentrated.Rapid column chromatography (petroleum ether/ethyl acetate = 4/1)Purification afforded compound 4-6 (370 mg, yield: 87%) as a colourless oil.

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Reference£º
Patent; Shanghai Dinuo Pharmaceutical Technology Co., Ltd.; Gao Daxin; Chen Shoujun; Liu Fengtao; (47 pag.)CN108148022; (2018); A;,
Tetrahydrofuran – Wikipedia
Tetrahydrofuran | (CH2)3CH2O – PubChem