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[ CAS No. 19879-84-6 ] {[proInfo.proName]}

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3d Animation Molecule Structure of 19879-84-6
Chemical Structure| 19879-84-6
Chemical Structure| 19879-84-6
Structure of 19879-84-6 * Storage: {[proInfo.prStorage]}
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Product Details of [ 19879-84-6 ]

CAS No. :19879-84-6 MDL No. :MFCD00063271
Formula : C14H20O9S Boiling Point : -
Linear Structure Formula :- InChI Key :SFOZKJGZNOBSHF-RGDJUOJXSA-N
M.W : 364.37 Pubchem ID :88293
Synonyms :

Calculated chemistry of [ 19879-84-6 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 24
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.71
Num. rotatable bonds : 9
Num. H-bond acceptors : 9.0
Num. H-bond donors : 0.0
Molar Refractivity : 81.45
TPSA : 153.23 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -7.79 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.71
Log Po/w (XLOGP3) : 1.03
Log Po/w (WLOGP) : 0.0
Log Po/w (MLOGP) : -0.3
Log Po/w (SILICOS-IT) : 0.26
Consensus Log Po/w : 0.74

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 1.0
Egan : 1.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -2.15
Solubility : 2.56 mg/ml ; 0.00701 mol/l
Class : Soluble
Log S (Ali) : -3.84
Solubility : 0.0529 mg/ml ; 0.000145 mol/l
Class : Soluble
Log S (SILICOS-IT) : -0.63
Solubility : 85.8 mg/ml ; 0.236 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 2.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 4.83

Safety of [ 19879-84-6 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 19879-84-6 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 19879-84-6 ]

[ 19879-84-6 ] Synthesis Path-Downstream   1~85

  • 1
  • [ 19879-84-6 ]
  • [ 41459-42-1 ]
  • [ 142913-90-4 ]
  • 2
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  • [ 2567-29-5 ]
  • [ 74590-52-6 ]
  • 3
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  • [ 2065-37-4 ]
  • [ 125791-35-7 ]
  • 5
  • [ 19879-84-6 ]
  • [ 113003-49-9 ]
  • Acetic acid (2S,3R,4S,5R,6R)-4,5-diacetoxy-6-acetoxymethyl-2-(N-hydroxy-anthracene-9-carboximidoylsulfanyl)-tetrahydro-pyran-3-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With triethylamine In diethyl ether; dichloromethane for 1h; Ambient temperature;
  • 6
  • [ 19879-84-6 ]
  • (Z)-N-hydroxy-2-phenylacetimidoyl chloride [ No CAS ]
  • [ 156258-43-4 ]
YieldReaction ConditionsOperation in experiment
83% With triethylamine; In diethyl ether; dichloromethane; at 20℃; for 2h;Inert atmosphere; General procedure: To stirred a solution of hydroxymoyl chloride 1 (1.5equiv) in dry Et2O/DCM (2:1, 45ml) was added a solution of 2,3,4,6-tetra-O-acetyl-beta-d-glucopyranosylthiol 6 (1equiv) in dry DCM (6ml). The resulting mixture was treated with Et3N (6equiv) in Et2O (12ml). The reaction mixture was stirred for 2h at rt under N2 then acidified with 1M H2SO4 (7ml/mmol of sugar). The mixture was left to stand for 10min and then separated. The aqueous phase was extracted with DCM (3×30ml). The combined organic layers were dried over MgSO4, filtered and the filtrate was concentrated under reduced pressure. The thiohydroxymate 7 was obtained by flash chromatography eluting with 0-3% MeOH/DCM.
  • 7
  • [ 41459-42-1 ]
  • [ 19879-84-6 ]
  • [ 142913-91-5 ]
  • 8
  • [ 40591-65-9 ]
  • [ 19879-84-6 ]
YieldReaction ConditionsOperation in experiment
99.3% With water; sodium sulfite; In ethyl acetate; at 40℃; for 1h;Inert atmosphere; A mixture of sodium sulfite (5.07 g, 40.22 mmol) in water (20 mL) and ethyl acetate (20 mL) was degassed under argon for ca. 10 minutes, then added to glucosyl isothiouronium salt 8 (19.71 g, 40.45 mmol). The biphasic solution was stirred rapidly at ca. 40 C with a stream of argon passing through it for one hour. The organic phase was then removed and concentrated to give the title compound as a white solid (14.64 g, 99.3%).
90% With sodium disulfite; In dichloromethane; water; for 1.5h;Heating / reflux; Example 2: 1-Thio-2,3,4,6-tetra-O-acetyl-ss-D-glucopyranose (2,3, 4, 6-Tetra-O-acetyl-ss-D-glucopyranosyl)-1-isothiouronium bromide (9.0 g, 18.8 mmol) and NA2S205 (4.93 g, 26.0 mmol) were added to a stirred mixture of DCM (150 mL) and water (70 mL). The mixture was heated to reflux under argon. After 1.5 h the reaction was cooled to room temperature (RT) and the phases were separated. The aqueous layer was re-extracted with DCM (3 x 50 mL). The combined organic layers were washed with water (50 mL), dried over MGS04, filtered and the solvent removed in vacuo to afford the title compound (6.14 g, 90%) as a white solid, mp 112-114C [Lit. 113-114C (R. J. Ferrier, R. H. FURNEAUX, CARBOHYDR. RES. 1977, 57, 73) ]; [alpha]D24+6. 3 (C, 1. 2 IN CHCL3) [LIT. [alpha]D20+5. 0 (C, 1.1 in CHCl3) (R. J. Ferrer, R. H. FURNEAUX, CARBOHYDR. RES. 1977, 57, 73)]; No.H (400 MHz, CDC13) 1.99, 2.00, 2.05, 2.06 (12H, 4 x s, 4 x CH3), 2.30 (IR d, JI, SH 10.2 Hz, SH), 3.71 (1H, ddd, J4, 5 10.0 Hz, J5,6 2.4 Hz, J5,6, 4. 7 Hz, H-5), 4. 10 (1H, dd, J6,6, 12.3 Hz, H-6), 4. 22 (1H, dd, H-6'), 4.53 (1H, at, J9, 9 Hz, EI-1), 4. 95 (1H, AT, J9.5 Hz, H-2), 5. 08 (1H, at, J 9. 8 HZ, H-4), 5.17 (1H, at, J 9. 4 Hz, H-3).
  • 9
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  • [ 698-16-8 ]
  • [ 150852-15-6 ]
YieldReaction ConditionsOperation in experiment
96% With triethylamine; In diethyl ether; dichloromethane; at 20℃; for 2h;Inert atmosphere; General procedure: To stirred a solution of hydroxymoyl chloride 1 (1.5equiv) in dry Et2O/DCM (2:1, 45ml) was added a solution of 2,3,4,6-tetra-O-acetyl-beta-d-glucopyranosylthiol 6 (1equiv) in dry DCM (6ml). The resulting mixture was treated with Et3N (6equiv) in Et2O (12ml). The reaction mixture was stirred for 2h at rt under N2 then acidified with 1M H2SO4 (7ml/mmol of sugar). The mixture was left to stand for 10min and then separated. The aqueous phase was extracted with DCM (3×30ml). The combined organic layers were dried over MgSO4, filtered and the filtrate was concentrated under reduced pressure. The thiohydroxymate 7 was obtained by flash chromatography eluting with 0-3% MeOH/DCM.
  • 10
  • [ 19879-84-6 ]
  • [ 25055-84-9 ]
  • [ 129451-60-1 ]
  • 12
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  • [ 7468-48-6 ]
  • [ 22626-90-0 ]
YieldReaction ConditionsOperation in experiment
83.1% Sodium hydride (0.576 g, 14.4 mmol) was added to a solution of 2,3,4,6-tetra-0-acetyl-l-thio-p-D- glucopyranose (5.01 g, 13.75 mmol) in dry THF (130 mL) at 0 C. The suspension was stirred under nitrogen until hydrogen formation had ceased. The resulting solution was then concentrated under reduced pressure, and the residue was dissolved in 60 mL of DMF. To this solution, 1 ,2,3,4-tetra-O- acetyl-6-deoxy-6-iodo-beta-D-glucopyranose (1 eq in 30 mL of DMF) was added. The mixture was stirred for 3 hours at room temperature under nitrogen, then concentrated under reduced pressure. A solution of the residue in DCM (250 mL) was washed with water (50 mL x 2), dried (Na2S04), and concentrated. Crystallization of the crude product was accomplished from EtOH. After drying, 7.23 g of the title compound as a white powder was obtained (79%). 1 HNMR showed that there was no alpha isomer. Mother liquor was purified by silica column. After removal of solvents, the residue was subjected to EtOH precipitation and 0.37 g of a white crystalline solid was obtained (4.1 %). Both materials showed the correct 1 HNMR and 13CNMR, identical to the reference.
  • 13
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  • [ 22568-49-6 ]
  • glucosinalbin thiohydroximate [ No CAS ]
YieldReaction ConditionsOperation in experiment
10% With triethylsilane; titanium tetrachloride; triethylamine In diethyl ether; dichloromethane at 20℃; for 3h;
  • 14
  • [ 19879-84-6 ]
  • [ 14918-69-5 ]
  • [ 141515-38-0 ]
  • 6-(Tetra-O-acetyl-β-D-glucopyranosyl-1-thio)-5,8-dihydroxy-2,3-dichloro-1,4-naphthoquinone [ No CAS ]
  • 2,3-Bis(Tetra-O-acetyl-β-D-glucopyranosyl-1-thio)-5,8-dihydroxy-1,4-naphthoquinone [ No CAS ]
  • 2,3,6-Tris(tetra-O-acetyl-β-D-glucopyranosyl-1-thio)-5,8-dihydroxy-1,4-naphthoquinone [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 36.8% 2: 16.3% 3: 3.5% 4: 1% With potassium carbonate In acetone at 20℃; for 0.5h;
  • 15
  • [ 19879-84-6 ]
  • [ 31309-08-7 ]
  • 2-(2',3',4',6'-tetra-O-acetyl-1'-thio-β-D-glucopyranosyl)-5-nitronicotinonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With potassium carbonate In acetone at 20℃; for 0.25h;
  • 17
  • [ 6806-56-0 ]
  • [ 19879-84-6 ]
YieldReaction ConditionsOperation in experiment
98% With sodium hydrogencarbonate; diothiothreitol; In N,N-dimethyl acetamide; at 20℃; for 1h; A method for synthesizing glycosyl mercaptans, comprising the steps of:(1) dissolving a thioacetyl-protected sugar, a thiol, and a weak base in an organic solvent so that theThe concentration of thioacetyl-protected sugar is 0.2 mM, the molar ratio of thioacetyl-protected sugar to thiol1: 1.5, the molar ratio of the thioacetyl-protected sugar to the weak base is 1: 0.1, and the raw materialMixed solution. The thioacetyl-protected sugar is 2,3,4,6-tetra-O-acetyl-1-S-acetyl-beta-D-pyranGlucose (600 mg, 1.48 mmol); the thiol is DL-1,4-dithiothreitol (342 mg,The weak base was NaHCO3 (13 mg, 0.15 mmol); the reaction solvent wasDimethylacetamide (7.4 ml). (2) The raw material mixture obtained in the step (1) was reacted at room temperature for 1 hour,Product extraction and purification should be obtained2,3,4,6-tetra-O-acetyl -? - D-glucopyranosylmercaptan. The specific operations of purification were: adding 50 ml of water, diluting with toluene, (3 x 100 ml)The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure.Glycosyl mercaptan 525mg, yield 98%. (3) The aqueous phase extracted in step (2) is extracted with NaCl and saturated, and extracted with ethyl acetate(3 × 100ml), concentrated, add 1 ? (w / w) K2CO3-MeOH solution dissolved at room temperature for 30min,Diatomite filtration, methanol washing, concentration, in DL-1,4-dithiothreitol, 315mg, recovery rate of 92%. .When the thiol used is DL-1,4-dithiothreitol (DTT), after the reaction is completed, the primary productPurity up to 95%, without purification steps can also be used directly.
With sodium hydrogencarbonate; diothiothreitol; In N,N-dimethyl acetamide; at 20℃; General procedure: Step 1: To a 0.15 M solution of thioacetate derivatives 1 (1.0 equiv) and DTT (1.5 equiv) in DMA was added NaHCO3 (0.2 equiv). The mixture was stirred at room temperature for an appropriate time until complete consumption of the starting material. The reaction mixture was poured into water and extracted with toluene for three times. The combined organic layers were washed with water, brine and concentrated to afford the crude product 2.
With sodium hydrogencarbonate; D,L-dithiothreitol; In N,N-dimethyl-formamide; at 20℃; for 25h;Inert atmosphere; General procedure: The S- deacetylation was conducted following by a reported method. Briefly, DMF (10 mL) was added to a mixture of thiolacetate derivatives 1b-6b (1.5 mmol), NaHCO3 (0.15 mmol) and DTT (2.5 mmol). The reaction mixture was stirred at RT for 1 h for secondary thiolacetate derivatives, and was stirred at RT for 24 h for primary thiolacetate derivatives under Ar(g) atmosphere. Then the mixture was poured into 100 mL water and extracted with toluene (80 mL × 3). The combined organic phase was washed with water (100 mL), and solvent was removed under vacuum. The crude product was used in the next step without further purification.
  • 18
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  • [ 558-42-9 ]
  • [ 857657-58-0 ]
  • 20
  • [ 19879-84-6 ]
  • [ 1471-17-6 ]
  • [ 757242-33-4 ]
YieldReaction ConditionsOperation in experiment
76% In methanol; at 20℃; for 6h;Ultraviolet light; A solution of tri-O-allylpentaerythritol (0.20 g; 0.78 mmol) and 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose (0.85 g; 2.34 mmol; 1 equiv.), in anhydrous methanol (15 mL) gas-free and under argon, is irradiated with ultraviolet light (250 nm) at ambient temperature for 6 hours. The solvent is evaporated and the residue is purified by silica gel column chromatography with ethyl acetate-petroleum ether 3:2. Thus 0.58 g (yield 76%) of a white solid is obtained, having the following characteristics: [alpha]D-26.6 (c 0.8; dichloromethane) mass spectrum (FAB+): m/z 1007 (100%, [M+Na]+)
  • 21
  • [ 19879-84-6 ]
  • [ 209115-33-3 ]
  • [ 876894-32-5 ]
YieldReaction ConditionsOperation in experiment
38% With 1,1'-azodicarbonyl-dipiperidine; trimethylphosphane In tetrahydrofuran at 20℃; for 3h;
  • 22
  • [ 134450-56-9 ]
  • [ 19879-84-6 ]
  • [ 1259331-73-1 ]
  • 23
  • [ 134450-56-9 ]
  • [ 19879-84-6 ]
  • 4,5-di(2,3,4,6-tetra-O-acetyl-1-thio-β-D-galactopyranosyl)phthalonitrile [ No CAS ]
  • 24
  • [ 19879-84-6 ]
  • [ 1263182-21-3 ]
  • [ 1263182-22-4 ]
YieldReaction ConditionsOperation in experiment
93% With 2,2-dimethoxy-2-phenylacetophenone; In dichloromethane; at 20℃; for 0.25h;UV-irradiation; To a solution of 17 (30 mg, 0.10 mmol) and 1 (44 mg, 0.12 mmol) in CH2Cl2 (2 mL) was added DPAP (1.4 mg, 0.01 mmol). The solution was irradiated at r. t. for 15 min under magnetic stirring and then concentrated. The residue was eluted from a column of silica gel with 2:1 cyclohexane-AcOEt to give 18 (62 mg, 93%) as an amorphous solid; [a]D = +35.7 (c 0.8, CHCl3). 1H NMR (300 MHz, CDCl3): d 5.37 (bd, 1H, J = 7.8 Hz, NH), 5.24 (dd, 1H, J2,3 = J3,4 = 9.4 Hz, H-3), 5.09 (dd, 1H, J4,5 = 9.8 Hz, H-4), 5.04 (dd, 1H, J1,2 = 10.0 Hz, H-2), 4.58-4.48 (m, 1H), 4.49 (d, 1H, H-1), 4.26 (dd, 1H, J5,6a = 4.7, J6a,6b = 12.5 Hz, H-6a), 4.23 (q, 2H, J = 7.1 Hz, CH2CH3), 4.14 (dd, 1H, J5,6b = 2.4 Hz, H-6b), 3.72 (ddd, 1H, H-5), 3.03-2.90 (m, 2H), 2.77-2.61 (m, 2H), 2.59-2.52 (m, 2H), 2.10, 2.08, 2.04, and 2.02 (4 s, 12H, 4 Ac), 1.75-1.65 (m, 4H), 1.46 (s, 9H, t-Bu), 1.31 (t, 3H, J = 7.1 Hz, CH2CH3). 13C NMR (75 MHz, CDCl3): d 171.0 (C), 170.6 (C), 170.1 (C), 169.4 (C), 155.1 (C), 83.4 (CH), 80.0 (C), 75.9 (CH), 73.8 (CH), 69.8 (CH), 68.2 (CH), 62.1 (CH2), 61.7 (CH2), 53.3 (CH), 34.5 (CH2), 32.1 (CH2), 29.3 (CH2), 28.3 (CH3), 20.7 (CH3), 20.6 (CH3), 14.1 (CH3). HRMS: m/z calcd for C28H45NNaO13S2 (M+Na)+ 690.2224, found 690.2226.
  • 25
  • [ 19879-84-6 ]
  • [ 75266-40-9 ]
  • [ 1263182-16-6 ]
YieldReaction ConditionsOperation in experiment
90% With 2,2-dimethoxy-2-phenylacetophenone; In dichloromethane; at 20℃; for 0.5h;UV-irradiation; The reaction was carried out in a glass vial (diameter: 1 cm; wall thickness: 0.65 mm), sealed with a natural rubber septum, located 2.5 cm away from the household UVA lamp apparatus equipped with four 15 W tubes (1.5 x 27 cm each). To a solution of alkene (0.10 mmol) and glycosyl thiol (0.12 mmol) in CH2Cl2 (1 mL) was added DPAP (0.01 mmol). The solution was irradiated at r. t. for 30 min under magnetic stirring and then concentrated. The residue was eluted from a column of silica gel to give the S-glycosyl amino acid derivative.
  • 26
  • [ 19879-84-6 ]
  • [ 367275-82-9 ]
  • [ 1263182-13-3 ]
YieldReaction ConditionsOperation in experiment
73% With 2,2-dimethoxy-2-phenylacetophenone; In dichloromethane; at 20℃; for 0.5h;UV-irradiation; The reaction was carried out in a glass vial (diameter: 1 cm; wall thickness: 0.65 mm), sealed with a natural rubber septum, located 2.5 cm away from the household UVA lamp apparatus equipped with four 15 W tubes (1.5 x 27 cm each). To a solution of alkene (0.10 mmol) and glycosyl thiol (0.12 mmol) in CH2Cl2 (1 mL) was added DPAP (0.01 mmol). The solution was irradiated at r. t. for 30 min under magnetic stirring and then concentrated. The residue was eluted from a column of silica gel to give the S-glycosyl amino acid derivative.
  • 27
  • [ 19879-84-6 ]
  • [ 21950-96-9 ]
  • [ 340960-70-5 ]
YieldReaction ConditionsOperation in experiment
86% With potassium carbonate; In water; ethyl acetate; at 20℃; for 1h;Inert atmosphere; General procedure: Unless otherwise stated, a mixture of sodium sulfite (ca. 0.100 mol) in H2O (50 mL) and EtOAc (50 mL) was degassed under argon for ca.10 min, then added to S-(2,3,4,6-tetra-O-acetyl-1-beta-D-glucopyranosyl)isothiouronium bromide (8; ca. 0.100 mol). The biphasic solution was stirred rapidly at r.t., with a stream of argon passing through it, until the precipitate had fully dissolved, then stirred for at least an additional15 min (total 1-1.5 h). The organic phase was removed to provide 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose (2) as asolution in EtOAc, which was used immediately. Separately, a solution of oxime (ca. 0.105 mol) in EtOAc (100 mL) was treated successively with concd HCl (0.40 mL, 4.7 mmol) and N-chlorosuccinimide (NCS, ca. 0.100 mol) and stirred for 1 h at r.t., upon which the blue colour disappeared (an exotherm was observed, with the internal temperature rising to ca. 50 C), to provide a solution of N-hydroxyimidoyl chloride. The N-hydroxyimidoyl chloride mixture was treated successively with the 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose solution, and a solution of K2CO3 (ca. 0.12 mol) in H2O (40 mL), then the mixture was stirred for 1 h at r.t. The mixture was separated, the organic phase was washed with a small quantity of 2.4 M HCl to fully acidify the product, then the organic phase was concentrated. The crude product was recrystallised from MeOH and H2O (2:1 (v/v)). The precipitate was collected by filtration, washed with H2O, then dried under vacuum to provide the thiohydroximate 9 as a white or off-white solid. The solid was contaminated with succinimide, with the amount quoted as determined by 1H NMR analysis; the values are in good agreement with those determined by elemental analysis (actualsulfur content vs calculated). A small quantity of product was recrystallised from MeOH and H2O to provide an analytical sample.
With triethylamine; In dichloromethane; at 20℃; for 3h; General procedure: 3-Phenylpropanal oxime (0.20 g, 1.3 mmol) was dissolved in CH2Cl2 (6 ml) and shaken with bleach (Fisher Scientific, sodium hypochlorite solution, 8% available chlorine, 2.5 mL, 4.0 mmol) in a separating funnel. Once the solution had changed from colourless to blue to yellow, the organic layer was added dropwise to a solution of acetylated thioglucose (0.29 g, 0.8 mmol) in CH2Cl2 (4 mL). The resulting solution was then treated with Et3N (0.4 mL, 2.7 mmol) and stirred at room temperature for 3 h. The solution was diluted with CH2Cl2 (5 mL) and treated with 0.5 M HCl (2 × 10 mL). The organic layer was separated, dried over MgSO4 and concentrated under reduced pressure. The crude product was then recrystallised from MeOH.
  • 28
  • [ 19879-84-6 ]
  • [ 92988-96-0 ]
  • [ 101540-18-5 ]
YieldReaction ConditionsOperation in experiment
95% With triethylamine; In tetrahydrofuran; General procedure: As reported previously, a solution of N-hydroxy-3-phenylpropanimidoyl chloride (9.24 g, 50.3 mmol) in THF (250 mL) was treated with 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose (12.60 g, 34.6 mmol) and triethylamine (34.0 ml, 0.24 mmol) and stirred overnight. The solution was poured onto ice-water (150 mL) and extracted using ethyl acetate (2 x 100 mL). The phases were separated, the organic phase was washed with water (100 mL), then dried, filtered and concentrated. The residue was purified by column chromatography (50% ethyl acetate in hexanes) to afford the title compound as a white solid (16.8 g, 95.0 %).
With triethylamine; In dichloromethane; at 20℃; for 3h; 3-Phenylpropanal oxime (0.20 g, 1.3 mmol) was dissolved in CH2Cl2 (6 ml) and shaken with bleach (Fisher Scientific, sodium hypochlorite solution, 8% available chlorine, 2.5 mL, 4.0 mmol) in a separating funnel. Once the solution had changed from colourless to blue to yellow, the organic layer was added dropwise to a solution of acetylated thioglucose (0.29 g, 0.8 mmol) in CH2Cl2 (4 mL). The resulting solution was then treated with Et3N (0.4 mL, 2.7 mmol) and stirred at room temperature for 3 h. The solution was diluted with CH2Cl2 (5 mL) and treated with 0.5 M HCl (2 × 10 mL). The organic layer was separated, dried over MgSO4 and concentrated under reduced pressure. The crude product was then recrystallised from MeOH to yield a white solid (0.31 g, 76%); mp 200-202 C (Lit.19 198 C); m/z 533.89 [M+Na]+; vmax (KBr)/cm-1 3316 (NOH), 1713 (CO), 1606 (CN); 1H NMR (300 MHz, CDCl3), 7.28-7.10 (5H, m, CHAr), 5.20-5.13 (1H, m, CH), 5.03-4.89 (3H, m, 3CH), 4.06 (1H, d, J = 11.9 Hz, CH26a), 4.02 (1H, d, J = 11.9 Hz, CH26b), 3.66-3.58 (1H, m, CH5), 2.96-2.64 (4H, m, 2CH27,8), 1.99 (3H, s, CH3), 1.96 (3H, s, CH3), 1.94 (3H, s, CH3), 1.85 (3H, s, CH3); 13C NMR (100 MHz, CDCl3) 171.2, 170.8, 169.9, 169.8 (CO), 152.2 (CN), 140.9 (CAr) 129.1, 128.7, 126.9 (5 × CHAr), 80.3 (CH1), 76.5 (CH5), 74.1 (CH3), 70.5 (CH2), 68.4 (CH4), 62.6 (CH26), 34.8 (CH27), 33.5 (CH28), 21.0-20.9 (4 × OC(O)CH3).
  • 29
  • [ 128-08-5 ]
  • [ 19879-84-6 ]
  • [ 1318852-98-0 ]
YieldReaction ConditionsOperation in experiment
65% To a stirred solution of 1a (0.5 g, 1.37 mmol in 5 mL EtOAc) AgOAc (0.23 g, 1.37 mmol) was added. After 40 min (TLC indicated consumption of the thiol) the mixture was cooled (0-4 C) and added to a cold (0-4 C) solution of N-bromosuccinimide (0.24 g, 1.37 mmol in 5 mL EtOAc), stirred at rt for more than 10 min, and filtered through Celite. Evaporation under reduced pressure followed by column chromatography (1:1 hexane/EtOAc) afforded 1c as a white crystal, 0.42 g (65%), mp 197-199 C; inlMMLBox -35.7 (c 0.51, CHCl3); 1H NMR (CDCl3, 500 MHz): delta 5.20 (t, 1H, H-3, J2,3 9.8 Hz); 5.07 (t, 1H, H-2); 4.92 (t, 1H, H-4); 4.70 (d, 1H, H-1, 3J1,2 9.8 Hz); 4.20 (dd, 1H, H-6a, J6a,6b 12.3 Hz, J5,6a 5.1 Hz); 4.14 (dd, 1H, H-6b, J6a,6b 12.0 Hz, J5,6b 2.5 Hz) 3.67 (m, 1H, H-5); 2.86 (s, 4H, CH2), 2.11, 2.08, 2.04, 2,03 (s, 12H, 4 × COCH3); 13C NMR (CDCl3, 125 MHz): delta 176.3 (CH2CO); 170.5, 170.0, 169.8, 169.2 (COCH3); 86.2 (C-1); 76.1 (C-5); 73.8 (C-3); 68.9 (C-2); 67.3 (C-4); 61.8 (C-6); 28.6 (CH2); 20.6, 20.5 (COCH3). Anal. Calcd for C18H23NO11S: C, 46.85; H, 5.02; N, 3.04; S, 6.95. Found: C, 47.34; H, 5.22; N, 3.02; S, 6.70. HRMS m/z Calcd for C18H23NO11S [M+Na]+: 484.0884. Found: 484.0862.
  • 30
  • [ 2439-85-2 ]
  • [ 19879-84-6 ]
  • [ 1318852-97-9 ]
YieldReaction ConditionsOperation in experiment
45% Starting from 0.5 g (1.37 mmol) of 1-thio-2,3,4,6-tetra-O-acetyl-alpha-d-mannopyranose (4a), the procedure described for 3a provided 0.32 g (45%) of 4b after purification by column chromatography (6:4 hexane/EtOAc). Syrup, inlMMLBox -20.6 (c 0.50, CHCl3); 1H NMR (CDCl3, 500 MHz): delta 7.95 (dd, 2H, Aryl-H), 7.81 (dd, 2H, Aryl-H); 5.53 (dd, 1H, H-2, J1,2 1.3 Hz, J2,3 4.0 Hz); 5.51 (s, 1H, H-1); 5.34 (t, 1H, H-4, J3,4 10.1 Hz); 5.18 (dd, 1H, H-3); 4.81 (m, 1H, H-5); 4.28 (dd, H-6a, J6a,6b 12.7 Hz, J5,6a 4.7 Hz); 4.00 (dd, H-6b, J5,6b 3.1 Hz); 2.13, 2.07, 1.99, 1.98 (s, 12H, 4 × COCH3); 13C NMR (CDCl3, 125 MHz): delta 170.4, 169.6, 169.5, 169.4 (COCH3); 167.2 (CO); 134.8, 131.8; 124.0 (Aryl-C), 85.53 (C-1); 70.4 (C-5); 69.6 (C-3); 67.2 (C-2); 65.4 (C-4); 61.8 (C-6); 20.6, 20.5, 20.4 (COCH3). Anal. Calcd for C22H23NO11S: C, 51.87; H, 4.52; N, 2.75; S, 6.29. Found: C, 51.89; H, 4.77; N, 2.80; S, 6.47.
  • 31
  • [ 2439-85-2 ]
  • [ 19879-84-6 ]
  • [ 1318852-94-6 ]
YieldReaction ConditionsOperation in experiment
80% To a stirred solution of 1-thio-2,3,4,6-tetra-O-acetyl-beta-d-glucopyranose 1a (1 g, 2.74 mmol) in 40 mL EtOAc, 0.455 g (2.74 mmol) AgOAc was added The reaction mixture was stirred at room temperature until TLC indicated consumption of the starting thiol (40 min), the solution cooled to 0-4 C and a cold solution of <strong>[2439-85-2]N-bromophthalimide</strong> (0.62 g, 2.74 mmol) in 20 mL EtOAc was added. After 10 min. the reaction mixture was filtered through Celite, evaporated under reduced pressure and the residue crystallized from MeOH to furnish 0.62 g of white solid. Evaporation of the mother liquor provided another 0.50 g of 1b after purification by column chromatography (6:4 hexane/EtOAc). Overall yield 1.12 g (80%), mp 172-175 C, inlMMLBox -32.5 (c 0.51, CHCl3); 1H NMR (CDCl3, 500 MHz): delta 7.95 (dd, 2H, Aryl-H) 7.82 (dd, Aryl-H); 5.22 (t, 1H, H-3); 5.06 (t, 1H, H-2, J3,4 9.0 Hz); 4.98 (t, 1H, H-4); 4.68 (d, 1H, H-1, J1,2 10.1 Hz); 4.18 (dd, 1H, H-6a, J6a,6b 12.1 Hz, J5,6a 5.0 Hz); 4.09 (dd, 1H, H-6b, J5,6b 2.3 Hz); 3.67 (m, 1H, H-5); 2.19, 2.01, 2.00, 1.96 (s, 12H, 4 × COCH3); 13C NMR (CDCl3, 125 MHz): delta 170.4, 169.9, 169.7, 169.2 (COCH3); 167.2 (CO); 134.8, 131.8, 124.0 (Aryl-C) 87.2 (C-1); 75.9 (C-5); 73.6 (C-3); 68.9 (C-2); 67.8 (C-4); 61.8 (C-6); 20.6, 20.5, 20.4 (COCH3). Anal. Calcd for C22H23NO11S: C, 51.87; H, 4.52; N, 2.75; S, 6.29. Found: C, 51.83; H, 4.78; S, 6.31; N, 2.80; HRMS m/z Calcd for C22H23NO11S [M+Na]+: 532.0884. Found: 532.0879.
  • 32
  • [ 2439-85-2 ]
  • [ 19879-84-6 ]
  • [ 1318852-95-7 ]
YieldReaction ConditionsOperation in experiment
63% This compound was prepared as described for 1b, starting from 1 g (2.74 mmol) of 1-thio-2,3,4,6-tetra-O-acetyl-beta-d-galactopyranose 2a. Overall yield 0.88 g (63%) of a white powder, mp 157-159 C, inlMMLBox -40.6 (c 0.50, CHCl3); 1H NMR (CDCl3, 500 MHz): delta 7.96 (dd, 2H, Aryl-H), 7.82 (dd, 2H, Aryl-H); 5.39 (d, 1H, H-4); 5.24 (t, 1H, H-2); 5.06 (dd, 1H, H-3, J3,4 3.2 Hz); 4.70 (d, 1H, H-1, J1,2 10.1 Hz); 4.08 (dd, 2H, H-6a,b, J6a,6b 11.3 Hz, J5,6a 6.8 Hz); 3.84 (m, 1H, H-5); 2.21, 2.13, 1.99, 1.91 (s, 12H, 4 × COCH3); 13C NMR (CDCl3, 125 MHz): delta 170.1, 170.0, 169.8 (COCH3); 167.2 (CO); 134.8, 131.8, 123.9 (Aryl-C); 88.6 (C-1); 74.4 (C-5); 71.5 (C-3); 66.8 (C-2); 66.0 (C-4); 61.1 (C-6); 20.7, 20.5, 20.4, 20.3 (COCH3). Anal. Calcd for C22H23NO11S: C, 51.87; H, 4.52; N, 2.75; S, 6.29. Found: C, 51.71; H, 4.49; N, 2.74; S, 6.24. HRMS m/z Calcd for C22H23NO11S [M+Na]+: 532.0884. Found: 532.0864.
  • 33
  • [ 19879-84-6 ]
  • [ 1445739-72-9 ]
  • [ 1445739-79-6 ]
YieldReaction ConditionsOperation in experiment
84% With acetic acid; In methanol; at 25 - 30℃; for 0.5h;Inert atmosphere; Flow reactor; Irradiation; General procedure: A photoreactor was set up using5 mL (for optimization reactions 2 mL) loop of FEP tubingaround a Pyrex and a medium pressure Hg lamp [26,43]. Arecirculating chiller (Huber Unistat 360, filled with spectroscopicallypure water as coolant) was used to maintain the reactor ata temperature of 25-30 C (for further details see SupportingInformation File 1). Using a syringe pump (Harvard PHD2000),a solution of DDS 1 (1.0 equiv), acetyl-protected thioglycosidesglycoside2-7 (1.5-2.0 equiv) and acetic acid (3 equiv) indegassed methanol was injected into the photoreactor. Theentire reactor output was collected and evaporated underreduced pressure to afford the crude material.
  • 34
  • [ 19879-84-6 ]
  • [ 2592-05-4 ]
  • [ 1421863-76-4 ]
YieldReaction ConditionsOperation in experiment
Stage #1: 1H-indole-3-carboxaldehyde oxime With pyridine; N-chloro-succinimide In dichloromethane at 0 - 20℃; Stage #2: tetraacetyl thioglucose With triethylamine In dichloromethane at 20℃; for 3h;
  • 35
  • [ 19755-53-4 ]
  • [ 19879-84-6 ]
  • [ 99800-58-5 ]
  • 36
  • [ 19879-84-6 ]
  • [ 1393083-66-3 ]
  • [ 1452840-27-5 ]
YieldReaction ConditionsOperation in experiment
78% With 2,3-dicyano-5,6-dichloro-p-benzoquinone; In dichloromethane; at 0℃; for 1h;Inert atmosphere; General procedure: To a1:1 mixture of the appropriate glycosyl thiols (0.20 mmol) in dry CH2Cl2(3 ml) was added DDQ (0.12 mmol) at 0 oC. After 30 minutes ofstirring, TLC analysis indicated residual starting material, so additional DDQ(0.10 mmol) was added. The reaction was left to stir for a further 30 minutesbefore concentration in vacuo. Theresulting residue was purified by flash chromatography.
  • 37
  • [ 19879-84-6 ]
  • [ 92988-96-0 ]
  • [ 75336-75-3 ]
YieldReaction ConditionsOperation in experiment
81% With triethylamine; In diethyl ether; dichloromethane; at 20℃; for 2h;Inert atmosphere; General procedure: To stirred a solution of hydroxymoyl chloride 1 (1.5equiv) in dry Et2O/DCM (2:1, 45ml) was added a solution of 2,3,4,6-tetra-O-acetyl-beta-d-glucopyranosylthiol 6 (1equiv) in dry DCM (6ml). The resulting mixture was treated with Et3N (6equiv) in Et2O (12ml). The reaction mixture was stirred for 2h at rt under N2 then acidified with 1M H2SO4 (7ml/mmol of sugar). The mixture was left to stand for 10min and then separated. The aqueous phase was extracted with DCM (3×30ml). The combined organic layers were dried over MgSO4, filtered and the filtrate was concentrated under reduced pressure. The thiohydroxymate 7 was obtained by flash chromatography eluting with 0-3% MeOH/DCM.
  • 38
  • [ 19879-84-6 ]
  • [ 105363-16-4 ]
  • [ 1454841-10-1 ]
YieldReaction ConditionsOperation in experiment
86% With triethylamine; In diethyl ether; dichloromethane; at 20℃; for 2h;Inert atmosphere; General procedure: To stirred a solution of hydroxymoyl chloride 1 (1.5equiv) in dry Et2O/DCM (2:1, 45ml) was added a solution of 2,3,4,6-tetra-O-acetyl-beta-d-glucopyranosylthiol 6 (1equiv) in dry DCM (6ml). The resulting mixture was treated with Et3N (6equiv) in Et2O (12ml). The reaction mixture was stirred for 2h at rt under N2 then acidified with 1M H2SO4 (7ml/mmol of sugar). The mixture was left to stand for 10min and then separated. The aqueous phase was extracted with DCM (3×30ml). The combined organic layers were dried over MgSO4, filtered and the filtrate was concentrated under reduced pressure. The thiohydroxymate 7 was obtained by flash chromatography eluting with 0-3% MeOH/DCM.
  • 39
  • [ 19879-84-6 ]
  • [ 105363-12-0 ]
  • [ 1454839-24-7 ]
YieldReaction ConditionsOperation in experiment
96% With triethylamine; In diethyl ether; dichloromethane; at 20℃; for 2h;Inert atmosphere; General procedure: To stirred a solution of hydroxymoyl chloride 1 (1.5equiv) in dry Et2O/DCM (2:1, 45ml) was added a solution of 2,3,4,6-tetra-O-acetyl-beta-d-glucopyranosylthiol 6 (1equiv) in dry DCM (6ml). The resulting mixture was treated with Et3N (6equiv) in Et2O (12ml). The reaction mixture was stirred for 2h at rt under N2 then acidified with 1M H2SO4 (7ml/mmol of sugar). The mixture was left to stand for 10min and then separated. The aqueous phase was extracted with DCM (3×30ml). The combined organic layers were dried over MgSO4, filtered and the filtrate was concentrated under reduced pressure. The thiohydroxymate 7 was obtained by flash chromatography eluting with 0-3% MeOH/DCM.
  • 40
  • [ 19879-84-6 ]
  • [ 1454839-23-6 ]
  • [ 1454839-25-8 ]
YieldReaction ConditionsOperation in experiment
86% With triethylamine; In diethyl ether; dichloromethane; at 20℃; for 2h;Inert atmosphere; General procedure: To stirred a solution of hydroxymoyl chloride 1 (1.5equiv) in dry Et2O/DCM (2:1, 45ml) was added a solution of 2,3,4,6-tetra-O-acetyl-beta-d-glucopyranosylthiol 6 (1equiv) in dry DCM (6ml). The resulting mixture was treated with Et3N (6equiv) in Et2O (12ml). The reaction mixture was stirred for 2h at rt under N2 then acidified with 1M H2SO4 (7ml/mmol of sugar). The mixture was left to stand for 10min and then separated. The aqueous phase was extracted with DCM (3×30ml). The combined organic layers were dried over MgSO4, filtered and the filtrate was concentrated under reduced pressure. The thiohydroxymate 7 was obtained by flash chromatography eluting with 0-3% MeOH/DCM.
  • 41
  • [ 19879-84-6 ]
  • 2,3-dichlorobenzohydroximoyl chloride [ No CAS ]
  • [ 1454839-26-9 ]
YieldReaction ConditionsOperation in experiment
90% With triethylamine; In diethyl ether; dichloromethane; at 20℃; for 2h;Inert atmosphere; General procedure: To stirred a solution of hydroxymoyl chloride 1 (1.5equiv) in dry Et2O/DCM (2:1, 45ml) was added a solution of 2,3,4,6-tetra-O-acetyl-beta-d-glucopyranosylthiol 6 (1equiv) in dry DCM (6ml). The resulting mixture was treated with Et3N (6equiv) in Et2O (12ml). The reaction mixture was stirred for 2h at rt under N2 then acidified with 1M H2SO4 (7ml/mmol of sugar). The mixture was left to stand for 10min and then separated. The aqueous phase was extracted with DCM (3×30ml). The combined organic layers were dried over MgSO4, filtered and the filtrate was concentrated under reduced pressure. The thiohydroxymate 7 was obtained by flash chromatography eluting with 0-3% MeOH/DCM.
  • 42
  • [ 19879-84-6 ]
  • [ 29203-58-5 ]
  • S-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-4-bromophenylthiohydroxamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With triethylamine; In diethyl ether; dichloromethane; at 20℃; for 2h;Inert atmosphere; General procedure: To stirred a solution of hydroxymoyl chloride 1 (1.5equiv) in dry Et2O/DCM (2:1, 45ml) was added a solution of 2,3,4,6-tetra-O-acetyl-beta-d-glucopyranosylthiol 6 (1equiv) in dry DCM (6ml). The resulting mixture was treated with Et3N (6equiv) in Et2O (12ml). The reaction mixture was stirred for 2h at rt under N2 then acidified with 1M H2SO4 (7ml/mmol of sugar). The mixture was left to stand for 10min and then separated. The aqueous phase was extracted with DCM (3×30ml). The combined organic layers were dried over MgSO4, filtered and the filtrate was concentrated under reduced pressure. The thiohydroxymate 7 was obtained by flash chromatography eluting with 0-3% MeOH/DCM.
  • 43
  • 1-phenyl-2,5-bis(2-pyridyl)phosphole gold chloride [ No CAS ]
  • [ 19879-84-6 ]
  • [ 1111864-58-4 ]
YieldReaction ConditionsOperation in experiment
70% Sodium hydride (37.7 mg, 1.5 mmol) was added to a solution of 1-thio-beta-d-glucose tetraacetate (272 mg, 0.75 mmol) in tetrahydrofuran (25 mL). The heterogeneous mixture was stirred for 1 h at room temperature. The solution was filtered and added to a tetrahydrofuran solution (20 mL) of 1-phenyl-2,5-bis(2-pyridyl)phosphole gold complex 1 (408 mg, 0.68 mmol) [3]. The solution was stirred for 90 min at room temperature, and all volatile materials were removed under vacuum. After purification by column chromatography on silica gel (diethyl ether/ethyl acetate: 7/3), complex 2 was obtained as a yellow powder (436 mg, yield 70%). A patent for GoPI-sugar was registered (EP1771181B1).
  • 44
  • [ 19879-84-6 ]
  • [4-(diphenylphosphino)-N,N-di(pyridin-2-yl)benzamide-κP]AuCl [ No CAS ]
  • [4-(diphenylphosphino)-N,N-di(pyridin-2-yl)benzamide-κP]Au[3,4,5-triacetyloxy-6-(acetyloxymethyl)oxane-2-thiolate] [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With potassium carbonate; In ethanol; water; at 20℃; for 18h;Schlenk technique; Inert atmosphere; Darkness; In a Schlenk tube under argon were introduced 336 mg (0.486 mmol, 1 eq.) of [4-(diphenylphosphino)-N,N-di(pyridin-2-yl)benzamide-kappaP]AuCl 2, 177 mg (0.486 mmol, 1 eq.) of 1-thio-beta-d-glucose tetraacetate and 72.4 mg (0.524 mmol, 1.08 eq.) of potassium carbonate (K2CO3). A degassed 1:1 mixture of ethanol and distilled water (10 mL) was added, and the reaction mixture was stirred 18 h at room temperature in the dark. The solvent was evaporated and degassed acetone was added. The salts were removed by filtration under argon; the filtrate was evaporated and dried to obtain the desired product 4 as a white powder (408 mg, 0.400 mmol, 82%).
  • 45
  • [ 19879-84-6 ]
  • bismuth 5,10,15-tris(pentafluorophenyl)corrole [ No CAS ]
  • 5,10,15-tris[2,3,5,6-tetrafluoro-4-(2,3,4,6-tetra-O-acetyl-1-S-D-glucopyranos-1-S-yl)phenyl]corrole [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With sodium hydride; In dimethyl sulfoxide; mineral oil; at 25℃; for 0.5h;Inert atmosphere; General procedure: Bismuth corrole 1 (40 mg, 40 mumol) and NaH (60% suspension inmineral oil, 30 equiv) were placed in a 50 mL 3-necked roundbottomedflask under argon. DMSO (30 mL) and S-nucleophile(3 equiv) were added and the reaction mixture was stirred for 25-35 min at r.t. The progress of the reaction was monitored by TLC(eluent: as denoted for column chromatography of each compound)and after complete conversion H2O (8 mL) was added to the mixture.To the H2O-DMSO phase was added sat. aq NH4Cl (15 mL)and the solution was extracted with CH2Cl2 (2 × 15 mL). The combinedorganic phases were washed with H2O (3 × 15 mL) and thesolvent was evaporated under reduced pressure.
  • 46
  • [ 19879-84-6 ]
  • [ 172876-96-9 ]
  • [ 127066-70-0 ]
  • 47
  • [ 19879-84-6 ]
  • [ 15529-90-5 ]
  • auranofin [ No CAS ]
YieldReaction ConditionsOperation in experiment
676 mg With potassium carbonate; In dichloromethane; water; at 0 - 20℃; for 1h; General procedure: To a solution of derivatives 1c-6c (1.05 mmol) and <strong>[15529-90-5]chloro(triethylphosphine)gold(I)</strong> (1.0 mmol) in DCM (4 mL), a solution of K2CO3 (1.2 mmol in 4 mL water) was added dropwise at 0 C. The mixture was stirred at RT for 1 h. Then the mixture was poured into 30 mL water, and extracted with DCM (30 mL × 3). The combined organic phase was dried with MgSO4 and filtered. After removing the solvent, the residue was purified by column chromatography to give the auranofin analogs 1-6.
  • 48
  • [ 19879-84-6 ]
  • (2-aminoethyldiphenylphosphine-κP)chloridogold(I) [ No CAS ]
  • 2-aminoethyldiphenylphosphane gold(I)thiolato-β-D-glucose tetraacetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% A Schlenk tube was charged under argon with thio-beta-dglucose tetraacetate (1 eq., 55 mg, 0.15 mmol) dissolved in degassed acetonitrile (5 mL). NaOH 1 M (1 eq., 0.16 mL,0.15 mmol) was added and the mixture was reacted 30 min at room temperature. The mixture was then transferred on a solution of 2-aminoethyldiphenylphosphane gold(I)chloride A (1 eq., 70 mg, 0.15 mmol) in dichloromethane(3 mL) at 0 C. After the end of the addition, the ice bath was removed and the mixture was reacted for 3 h at roomtemperature. After removal of the solvents under vacuum and redissolution in dichloromethane, the solution was filtered through Celite. Upon removal of dichloromethane under vacuum, and rinsing with pentane, an off-white product was obtained as a powder (108 mg, 90 % yield).1H NMR (CDCl3, 300 K, 600.23 MHz): 1.87 (broad s, 2H, NH2), 1.94 (s, 3 H, CH3C(O)), 1.98 (s, 3 H, CH3C(O)),2.01 (s, 3 H, CH3C(O)), 2.07 (s, 3 H, CH3C(O)), 2.69(m, 2H, P-CH2), 3.10 (m, 2 H, N-CH2), 3.76 (dd, 1 H,3JH-H = 2.4 Hz, 3JH-H = 9.0 Hz, CHsugar), 4.11 (dd, 1 H,2JH-H = 12.6 Hz, 3JH-H = 2.4 Hz, CH2-sugar), 4.23 (dd, 1H, 2JH-H = 12.6 Hz, 3JH-H = 9.0 Hz, CH2-sugar), 5.06-5.17(m, 4 H, 4 CHsugar), 7.47-7.51 (m, 6 H, 4 CHmeta-Ph + 2CHpara-Ph), 7.69-7.75 (m, 4 H, 4 CHortho-Ph). 13C{1H} NMR(CDCl3, 300 K, 150.94 MHz): 20.8 (s, CH3C(O)), 20.9 (s,CH3C(O)), 21.0 (s, CH3C(O)), 21.3 (s, CH3C(O)), 32.1(d, 1JP-C = 34.7 Hz, CH2-P), 38.6 (d, 2JP-C = 7.5 Hz,CH2-NH2), 63.0 (s, CH2-sugar), 69.1 (s, CHsugar), 74.4(s, CHsugar), 76.0 (s, CHsugar), 77.9 (s, CHsugar), 83.4 (s,CHsugar), 129.4 (d, 3JP-C = 3.0 Hz, CHmeta), 129.5 (d,3JP-C = 3.0 Hz, CHmeta), 130.0 (d, 1JP-C = 13.6 Hz, Cipso),130.4 (d, 1JP-C = 13.6 Hz, Cipso), 131.8 (s, CHpara), 131.9(s, CHpara), 133.4 (d, 2JP-C = 7.5 Hz, CHortho), 133.5 (d,2JP-C = 7.5 Hz, CHortho), 169.8 (s, C(O)), 170.0 (s, C(O)),170.4 (s, C(O)), 170.9 (s, C(O)). 31P{1H} NMR (CDCl3,300 K, 242.96 MHz): 29.4 (broad s, P-Au-S). IR (ATR,cm-1): 2945, 1740, 1436, 1368, 1218, 1102, 1030, 519,487, 373, 215. ESI-MS (DCM/MeOH), positive mode exact mass for [C28H35AuNO9S.H]+ (790.15084): measuredm/z 790.14896 [M + H]+. Anal. Calc. for C28H35Au-NO9PS.H2O: C, 41.64, H, 4.62, N, 1.73, S, 3.97 %. Found:C, 41.63, H, 4.80, N, 1.73, S, 3.39 %
  • 49
  • [ 19879-84-6 ]
  • μ-(1-methyl-3-{4-[(2-diphenylphosphinoethyl)-κP-carbamoyl]benzyl}imidazol-2-ylidene)-κC-bis(chlorido)gold(I) [ No CAS ]
  • 1-methyl-3-(4-((diphenylphosphane gold(I)thiolato-β-D-glucose tetraacetate)ethylcarbamoyl)benzyl)imidazole-2-ylidene gold(I) thiolato-β-D-glucose tetraacetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% A Schlenk tube was charged under argon with thio-beta-d-glucose tetraacetate (2 eq., 50 mg, 0.139 mmol) dissolved in degassed acetone (3 mL). NaOH 1 M (2 eq., 0.14 mL,0.139 mmol) was added and the mixture and reacted 30 min at room temperature in the dark. The mixture was then transferred on a solution of 2 (1 eq., 62 mg, 0.069 mmol) in degassed acetone (5 mL) at 0 C. After the end of the addition,the ice bath was removed and the mixture was reacted for 3 h at room temperature in the dark. After removal of the acetone under vacuum and redissolution in dichloromethane,the solution was filtered through Celite. Upon concentration under reduced pressure, and addition of a large amount of pentane, an off-white precipitate formed which after drying under vacuum gave the product with two molecules of water as a white powder (85 mg, 79 %yield). 1H NMR (CDCl3, 300 K, 300.13 MHz): 1.91 (s, 6H, 2 × O(O)C-CH3), 1.93 (s, 6 H, 2 × O(O)C-CH3), 1.99(s, 6 H, 2 × O(O)C-CH3), 2.04 (s, 6 H, 2 × O(O)C-CH3),2.79-2.87 (m, 1 H, CH2-P), 2.99-3.08 (m, 1 H, CH2-P),3.73-3.82 (m, 4 H, CH2-NH + 2 × O-CHsugar-CH2), 3.86(s, 3 H, N-CH3), 4.07 (d, 2 H, 2JH-H = 10.2 Hz, 2 × CH2-sugar), 4.17 (dd, 1 H, 2JH-H = 10.2 Hz, 3JH-H = 4.8 Hz,2 × CH2-sugar), 5.09 (broad s, 8 H, 2 × 4 CHsugar), 5.34(d, 2JH-H = 15.3 Hz, CH2-Bz), 5.50 (d, 2JH-H = 15.3 Hz,CH2-Bz), 6.90 (d, 1 H, 3JH-H = 1.8 Hz, CHIm), 6.93 (d, 1H, 3JH-H = 1.8 Hz, CHIm), 7.34 (d, 2 H, 3JH-H = 8.4 Hz,2 × CHp-C6H4), 7.40-7.43 (m, 6 H, 2 × CHpara-Ph + 2 × 2 × CHortho-Ph), 7.66 (broad t, 3JH-H = 3.6 Hz,NH), 7.69-7.81 (m, 6 H, 2 × CHp-C6H4 + 2 × 2 × CHmeta-Ph). 13C {1H} NMR (CDCl3, 300 K, 125.77 MHz): 20.8 (s,O(O)C-CH3), 20.9 (s, O(O)C-CH3), 21.3 (s, O(O)C-CH3),28.0 (d, 1JP-C = 33.9 Hz, CH2-P), 37.2 (d, 2JP-C = 6.3 Hz,CH2-NH), 38.1 (s, N-CH3), 54.2 (s, N-CH2), 62.9 (s, CH2-sugar), 69.1 (broad s, CHsugar), 74.3 (s, CHsugar), 75.8 (s,CHsugar), 78.0 (broad s, CHsugar), 83.3 (broad s, CHsugar),120.6 (s, CHIm), 122.4 (s, CHIm), 127.9 (s, CHp-C6H4), 128.0(s, CHp-C6H4), 129.3 (d, 2JP-C = 10.1 Hz, CHortho-Ph), 129.4(d, 2JP-C = 10.1 Hz, CHortho-Ph), 129.8 (d, 1JP-C = 25.2 Hz,CHipso-Ph), 130.2 (d, 1JP-C = 25.2 Hz, CHipso-Ph), 131.8(d, 4JP-C = 2.5 Hz, CHpara-Ph), 131.9 (d, 4JP-C = 2.5 Hz,CHpara-Ph), 133.1 (d, 3JP-C = 13.8 Hz, CHmeta-Ph), 133.4 (d,3JP-C = 13.8 Hz, CHmeta-Ph), 134.1 (s, Cquat-p-C6H4), 139.1 (s,Cquat-p-C6H4), 167.1 (s, C(O)-NH), 169.9 (s, Ccarbene), 170.2 (s, C(O)O), 170.8 (s, C(O)O). 31P{1H} NMR (CDCl3,300 K, 202.45 MHz): 30.7 (broad s, P-Au-S). FT-IR(ATR, cm-1): 1740, 1658, 1534, 1435, 1367, 1217, 1030,602, 372, 216. ESI-MS (H2O/MeOH), positive mode exactmass for [C54H64Au2N3O19PS2Na]+ (1570.25363): measuredm/z 1570.26001 [M + Na]+ (see footnote 1). Anal.Calc. for C54H64Au2N3O19PS2.2H2O: C, 40.94, H, 4.33,N, 2.65, S, 4.05 %. Found: C, 40.53, H, 4.31, N, 2.84, S,3.14 %
  • 50
  • [ 19879-84-6 ]
  • [ 165534-79-2 ]
  • dimethyl 2-(((2S,3R,4S,5R,6R)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-yl)thio)terephthalate [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% With palladium diacetate; triethylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 100℃; for 1h; Inert atmosphere; Schlenk technique; Sealed tube;
  • 51
  • [ 19879-84-6 ]
  • [ 103440-52-4 ]
  • (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((2-(methoxycarbonyl)-4-methylphenyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With palladium diacetate; triethylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 100℃; for 1h; Inert atmosphere; Schlenk technique; Sealed tube;
  • 52
  • [ 19879-84-6 ]
  • [ 181765-85-5 ]
  • (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((5-chloro-2-(methoxycarbonyl)phenyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate [ No CAS ]
  • 53
  • [ 19879-84-6 ]
  • [ 181765-85-5 ]
  • (2R,3S,4S,4aR,11aS)-9-chloro-3,4-dihydroxy-2-(hydroxymethyl)-2,3,4,4a-tetrahydrobenzo[e]pyrano[3,2-b][1,4]oxathiepin-6(11aH)-one [ No CAS ]
  • 54
  • [ 57641-66-4 ]
  • [ 19879-84-6 ]
  • C18H28O11S [ No CAS ]
  • 55
  • [ 57641-67-5 ]
  • [ 19879-84-6 ]
  • [ 132156-09-3 ]
  • 56
  • [ 14243-64-2 ]
  • [ 19879-84-6 ]
  • (2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranosato)(triphenylphosphine) gold(I) [ No CAS ]
  • 57
  • [ 19879-84-6 ]
  • [ 29892-37-3 ]
  • [ 23743-26-2 ]
  • C54H86Au2O18P2S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% To a solution of 1,2-bis (dicyclohexylphosphino) ethane (50 mg, 118.31 [mu] mol)In dichloromethane (5 mL) was addedDimethyl sulfideEther chlorideGoldChloro (dimethyl sulfide) gold (I)(69.7 mg, 236.62 [mu] mol). Under argon at room temperature for 2 hours.Followed by an aqueous solution of potassium carbonate (34.3 mg, 248.46 μmol)1-thio-β-D-glucose tetraacetate(90.6 mg, 248.46 [mu] mol)Of methylene chloride solution. After stirring at room temperature for 2 hours, the TLC reaction was completed.After dilution with dichloromethane, the mixture was washed twice with saturated brine (10 mL x 2)The organic phase was dried over anhydrous sodium sulfate and evaporated to dryness.Column chromatography (PE / EA = 1/2) was separated by 1182,White foamy compound, 108 mg, yield 70%.
  • 58
  • [ 19879-84-6 ]
  • [ 211680-78-3 ]
  • C31H30AuNO9S [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With sodium carbonate; In dichloromethane; at 20℃; for 1.5h;Inert atmosphere; Schlenk technique; Complex 1 (1eq., 50mg, 0.115mmol), is added to thio-beta-d-glucose tetraacetate (1eq., 41.9mg, 0.115mmol) and Na2CO3 (5eq., 61mg, 0.575mmol) in dichloromethane (20mL). The suspension is stirred for 1.5h at room temperature. The solution is filtered through Celite and concentrated under reduced pressure. Upon cooling and subsequent addition of pentane a light yellow precipitate is formed which is filtered, washed with diethylether and n-pentane and dried under reduced pressure (78.96 mg, 0.10 mmol, 87% yield). 1H NMR (500MHz, Acetone-d6) delta 8.34-7.69 (m, 5H, Ha,b,c), 7.61-7.14 (m, 6H, Hd,e,f), 5.20-5.10 (m, 2H, 2 CH), 4.98 (m, 1H, CH), 4.89 (t, J=9.4Hz, 1H, CH), 4.79 (t, J=9.7Hz, 1H, CH), 4.15 (dd, J=12.3Hz, 2.1Hz, 1H, CH2-sugar), 4.02 (dd, J=12.3Hz, 5.6Hz, 1H, CH2-sugar), 1.96 (s, 3H, OAc), 1.94 (s, 3H, OAc), 1.86 (s, 3H, OAc), 1.77 (s, 3H, OAc). Positive ESI-MS (acetone): m/z=790.1442 [M+H]+ (calcd for C31H31AuNO9S: 790.1385). Anal. Calc. for C31H30AuNO9S: C, 47.15; H 3.83; N, 1.77; S, 4.06%. Found: C, 47.01; H, 3.68; N, 1.85; S, 3.75%.
  • 59
  • [ 19879-84-6 ]
  • [ 23051-08-3 ]
  • S-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-8-hydroxy-2-methylquinoline-7-carbothioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% With benzotriazol-1-ol; diisopropyl-carbodiimide; In pyridine; at 20℃; for 0.5h; General procedure: Procedure B. 2,3,4,6-Tetra-O-acetyl-1-thio-beta-d-glucopyranose 6 or 2,3,4,6-tetra-O-acetyl-1-thio-beta-d-galactopyranose 7 (0.1g, 0.274mmol) and quinaldine derivative 1 or 2 (0.055g, 0.274mmol) were dissolved in pyridine (3mL). The DIC (0.045mL, 0.274mmol) and HOBt (0.005g, 0.04mmol) were added to this mixture. The resulting mixture was left on the magnetic stirrer at room temperature. The reaction progress was monitored on TLC in an eluents system-toluene:AcOEt (2:1). Then, the reaction mixture was diluted with toluene, the solvents were evaporated and the residue was transferred to 2mL of toluene and the crude products were purified by column chromatography (toluene: AcOEt; gradient: 5:1 to 1:2) to produce products 17-20.
  • 60
  • [ 23051-08-3 ]
  • [ 19879-84-6 ]
  • S-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-8-hydroxy-2-methylquinoline-7-carbothioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
44% With benzotriazol-1-ol; diisopropyl-carbodiimide; In pyridine; at 20℃; for 3h; General procedure: Procedure B. 2,3,4,6-Tetra-O-acetyl-1-thio-beta-d-glucopyranose 6 or 2,3,4,6-tetra-O-acetyl-1-thio-beta-d-galactopyranose 7 (0.1g, 0.274mmol) and quinaldine derivative 1 or 2 (0.055g, 0.274mmol) were dissolved in pyridine (3mL). The DIC (0.045mL, 0.274mmol) and HOBt (0.005g, 0.04mmol) were added to this mixture. The resulting mixture was left on the magnetic stirrer at room temperature. The reaction progress was monitored on TLC in an eluents system-toluene:AcOEt (2:1). Then, the reaction mixture was diluted with toluene, the solvents were evaporated and the residue was transferred to 2mL of toluene and the crude products were purified by column chromatography (toluene: AcOEt; gradient: 5:1 to 1:2) to produce products 17-20.
  • 61
  • [ 19879-84-6 ]
  • (Z)-2,3,3-trifluoro-1-(p-tolylsulfonyl)prop-1-ene [ No CAS ]
  • 1-S-thio-[(Z)-2'-(3,3-difluoro-2-tosylprop-1-en-1-yl)-2,3,4,6-tetra-O-acetyl-β-D-glucopyranose] [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With triethylamine; In chloroform; at 20℃; for 2h; General procedure: To a solution of beta-fluorovinyl sulfones 2a,b (2 mmol) in anhydrous CHCl3 (15 mL)was added 2,3,4,6-tetra-O-acetyl-1-beta-thio-D-glucopyranose 8 (0.73 g, 2 mmol) andEt3N (0.2 g, 2 mmol) at room temperature. The reaction mixture was stirred 2 h(until 19F NMR spectra displayed complete consumption of the starting material).Then the mixture was diluted with CH2Cl2 (25 mL), water (25 mL) and extractedwith CH2Cl2 (2 × 25 mL). The organic phase was separated, dried over Na2SO4and evaporated under reduced pressure to give crude 9a,b (5/95 ratio of the E/Zisomers)with 98% yield. Products 9a and 9b were isolated in the pure state in Zisomericforms by recrystallization from MeOH.
  • 62
  • [ 19879-84-6 ]
  • [ 1024-99-3 ]
  • (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((1-((2R,3R,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-5-yl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate [ No CAS ]
  • 63
  • [ 19879-84-6 ]
  • [ 1024-99-3 ]
  • (2R,3S,4S,5R,6S)-2-(acetoxymethyl)-6-((1-((2R,3R,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-5-yl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate [ No CAS ]
  • 64
  • [ 19879-84-6 ]
  • [ 701-72-4 ]
  • [ 5149-26-8 ]
YieldReaction ConditionsOperation in experiment
70% With potassium carbonate; In water; ethyl acetate; at 20℃; for 1h;Inert atmosphere; A mixture of sodium sulfite (408 mg, 3.24 mmol) in H2O (5 mL) and EtOAc (5 mL) was degassed under argon for ca. 10 min, then added to glucosylisothiouronium salt 8 (1.46 g, 3.00 mmol). The biphasic solution was stirred rapidly at r.t., with a stream of argon passing throughit, until the precipitate had fully dissolved, then stirred for an additional 15 min (total 1.5 h). The organic phase was removed to provide thiosugar 2 as a solution in EtOAc, which was used immediately. Separately, a solution of oxime 5a (420 mg, 3.11 mmol) in EtOAc (3 mL) was treated successively with pyridine (10 muL, 0.1 mmol) and NCS (398 mg, 2.98 mmol), and stirred for 4 h at 50 C, to provide a solution of N-hydroxy-2-phenylacetimidoyl chloride (4a). The imidoyl chloride 4a mixture was treated successively with the thiosugar 2 solution, and a solution of K2CO3 (496 mg, 3.59 mmol) in H2O (2 mL), then the mixture was stirred for 1 h. The mixture was separated, the organic phase was washed with a small quantity of 2.4 M HCl (1 mL, 2.4 mmol), then the organic phase was concentrated. The crude product was recrystallised from MeOH (2 mL) and H2O (1 mL), with the precipitate washed with additional H2O (1 mL), and dried under vacuum to provide compound 9a as a white solid with ca. 2.1% (w/w) succinimide (1.07 g, 70 %). A second recrystallisation from MeOH and H2O provided the product with no observable succinimide impurity. Mp 163-164 C (Lit.15 163-164 C); Rf = 0.50 (hexanes-EtOAc, 1:1). IR: 3366, 1750, 1741, 1729, 1381, 1229, 1054, 976, 916, 707 cm-1. 1H NMR (400 MHz, DMSO-d6): delta = 11.45 (s, 1 H), 7.35-7.28 (m, 4 H),7.23 (t, J = 6.9 Hz, 1 H), 5.37 (d, J = 10.1 Hz, 1 H), 5.31 (t, J = 9.4 Hz, 1H), 4.92 (t, J = 9.7 Hz, 1 H), 4.85 (t, J = 9.7 Hz, 1 H), 4.07 (dd, J = 12.1, 5.6Hz, 1 H), 3.99 (ddd, J = 9.8, 5.7, 1.8 Hz, 1 H), 3.90 (s, 2 H), 3.85 (dd,J = 12.0, 1.7 Hz, 1 H), 1.98 (s, 3 H), 1.97 (s, 3 H), 1.96 (s, 3 H), 1.94 (s, 3 H). 13C NMR (100 MHz, DMSO-d6): delta = 169.8, 169.4, 169.2, 168.9, 148.6,136.6, 128.7, 128.3, 126.5, 78.2, 74.3, 72.8, 69.7, 67.8, 61.8, 37.2, 20.4,20.29, 20.25, 20.2. HRMS-TOF: m/z [M + H]+ calcd for C22H28NO10S+: 498.1428; found: 498.1443.
  • 65
  • [ 19879-84-6 ]
  • [ 41542-29-4 ]
  • S-(2',3',4',6'-tetra-O-acetyl-1-β-D-glucopyranosyl)butanethiohydroximate [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% With potassium carbonate; In water; ethyl acetate; at 20℃; for 1h;Inert atmosphere; General procedure: Unless otherwise stated, a mixture of sodium sulfite (ca. 0.100 mol) in H2O (50 mL) and EtOAc (50 mL) was degassed under argon for ca.10 min, then added to S-(2,3,4,6-tetra-O-acetyl-1-beta-D-glucopyranosyl)isothiouronium bromide (8; ca. 0.100 mol). The biphasic solution was stirred rapidly at r.t., with a stream of argon passing through it, until the precipitate had fully dissolved, then stirred for at least an additional15 min (total 1-1.5 h). The organic phase was removed to provide 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose (2) as asolution in EtOAc, which was used immediately. Separately, a solution of oxime (ca. 0.105 mol) in EtOAc (100 mL) was treated successively with concd HCl (0.40 mL, 4.7 mmol) and N-chlorosuccinimide (NCS, ca. 0.100 mol) and stirred for 1 h at r.t., upon which the blue colour disappeared (an exotherm was observed, with the internal temperature rising to ca. 50 C), to provide a solution of N-hydroxyimidoyl chloride. The N-hydroxyimidoyl chloride mixture was treated successively with the 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose solution, and a solution of K2CO3 (ca. 0.12 mol) in H2O (40 mL), then the mixture was stirred for 1 h at r.t. The mixture was separated, the organic phase was washed with a small quantity of 2.4 M HCl to fully acidify the product, then the organic phase was concentrated. The crude product was recrystallised from MeOH and H2O (2:1 (v/v)). The precipitate was collected by filtration, washed with H2O, then dried under vacuum to provide the thiohydroximate 9 as a white or off-white solid. The solid was contaminated with succinimide, with the amount quoted as determined by 1H NMR analysis; the values are in good agreement with those determined by elemental analysis (actualsulfur content vs calculated). A small quantity of product was recrystallised from MeOH and H2O to provide an analytical sample.
  • 66
  • [ 19879-84-6 ]
  • [ 87488-23-1 ]
  • S-(2',3',4',6'-tetra-O-acetyl-1-β-D-glucopyranosyl)-2-hexanethiohydroximate [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With potassium carbonate; In water; ethyl acetate; at 20℃; for 1h;Inert atmosphere; General procedure: Unless otherwise stated, a mixture of sodium sulfite (ca. 0.100 mol) in H2O (50 mL) and EtOAc (50 mL) was degassed under argon for ca.10 min, then added to S-(2,3,4,6-tetra-O-acetyl-1-beta-D-glucopyranosyl)isothiouronium bromide (8; ca. 0.100 mol). The biphasic solution was stirred rapidly at r.t., with a stream of argon passing through it, until the precipitate had fully dissolved, then stirred for at least an additional15 min (total 1-1.5 h). The organic phase was removed to provide 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose (2) as asolution in EtOAc, which was used immediately. Separately, a solution of oxime (ca. 0.105 mol) in EtOAc (100 mL) was treated successively with concd HCl (0.40 mL, 4.7 mmol) and N-chlorosuccinimide (NCS, ca. 0.100 mol) and stirred for 1 h at r.t., upon which the blue colour disappeared (an exotherm was observed, with the internal temperature rising to ca. 50 C), to provide a solution of N-hydroxyimidoyl chloride. The N-hydroxyimidoyl chloride mixture was treated successively with the 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose solution, and a solution of K2CO3 (ca. 0.12 mol) in H2O (40 mL), then the mixture was stirred for 1 h at r.t. The mixture was separated, the organic phase was washed with a small quantity of 2.4 M HCl to fully acidify the product, then the organic phase was concentrated. The crude product was recrystallised from MeOH and H2O (2:1 (v/v)). The precipitate was collected by filtration, washed with H2O, then dried under vacuum to provide the thiohydroximate 9 as a white or off-white solid. The solid was contaminated with succinimide, with the amount quoted as determined by 1H NMR analysis; the values are in good agreement with those determined by elemental analysis (actualsulfur content vs calculated). A small quantity of product was recrystallised from MeOH and H2O to provide an analytical sample.
  • 67
  • [ 19879-84-6 ]
  • [ 82565-68-2 ]
  • C38H39NO13S [ No CAS ]
  • 68
  • [ 19879-84-6 ]
  • [ 17356-09-1 ]
  • (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((4-isopropylphenyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate; diisopropylammonium bis(catecholato)isobutylsilicate; tetraaqua[4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]nickel(II) chloride In N,N-dimethyl-formamide at 25℃; for 24h; Inert atmosphere; Irradiation; Sealed tube;
  • 69
  • [ 19879-84-6 ]
  • [ 15278-97-4 ]
  • (2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranosato)(trimethylphosphine) gold(I) [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With potassium carbonate; In dichloromethane; water; at 0 - 20℃; General procedure: To a solution of chloro(triethylphosphine)gold(I) (1.0 mmol) and thiols (1.05 mmol) in toluene or DCM (4 mL), DBU (1.2 mmol in 1 mL of toluene or DCM) was added dropwise. The mixture was stirred at RT for 2 h. The mixture was concentrated, after which the residue was purified by column chromatography to give auranofin analogs 8, 18, 19, 21-23, 35-40.
  • 70
  • [ 15529-90-5 ]
  • [ 19879-84-6 ]
  • [ 99395-46-7 ]
YieldReaction ConditionsOperation in experiment
96% With potassium carbonate; In dichloromethane; water; at 0 - 20℃; for 1h; General procedure: To a solution of derivatives 1c-6c (1.05 mmol) and <strong>[15529-90-5]chloro(triethylphosphine)gold(I)</strong> (1.0 mmol) in DCM (4 mL), a solution of K2CO3 (1.2 mmol in 4 mL water) was added dropwise at 0 C. The mixture was stirred at RT for 1 h. Then the mixture was poured into 30 mL water, and extracted with DCM (30 mL × 3). The combined organic phase was dried with MgSO4 and filtered. After removing the solvent, the residue was purified by column chromatography to give the auranofin analogs 1-6.
  • 71
  • [ 19879-84-6 ]
  • C29H44N4O13 [ No CAS ]
  • C42H62N4O22S [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With 2,2-dimethoxy-2-phenylacetophenone; In dichloromethane; at 20℃; for 0.5h;UV-irradiation; Weigh out the compound Boc-AMP-Glu-ene (1.00g, 1.52mmol) and beta-D-glucose thiol compound (Glu-SH) (0.67g, 1.83mmol) in 4ml of dichloromethane, then weigh benzoin Methyl ether (DMPA) (0.016g, 0.06mmol) was added to the above reaction solution, and after stirring and dissolving, the reaction solution was irradiated at 365nm ultraviolet light for 30min at room temperature. TLC tracking detection. After the reaction was completed, the organic phase was washed with dichloromethane / water, and the organic phase was dried over anhydrous sodium sulfate. Silica gel powder was added and the sample was spin-dried. Eluent: PE / EA (v / v) = 2: 1), 1.36 g of colorless viscous substance (compound Boc-AMP-Glu-Glu) was isolated with a yield of 89%. The hydrogen and carbon spectra of Boc-AMP-Glu-Glu are shown in Figures 3 and 4, respectively.
  • 72
  • [ 19879-84-6 ]
  • C29H44N4O13 [ No CAS ]
  • C42H62N4O22S [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With 2,2-dimethoxy-2-phenylacetophenone; In dichloromethane; at 20℃; for 0.5h;UV-irradiation; Weigh out the compounds Boc-AMP-Gal-ene (0.50g, 0.761mmol) and beta-D-glucose thiol compound (Glu-SH) (0.33g, 0.91mmol) in 2mL of dichloromethane, then weigh benzoin Methyl ether (DMPA) (7.8 mg, 0.03 mmol) was added to the above reaction solution. After stirring and dissolving, the reaction solution was irradiated with UV light at 365 nm for 30 minutes at room temperature, followed by TLC. After the reaction was completed, the mixture was washed with dichloromethane / water, and the organic phase was dried over anhydrous sodium sulfate, and silica gel powder was added to directly spin dry the sample. silica gel column chromatography (developing solvent: PE / EA (v / v) = 1: 1, eluent: PE / EA (v / v) = 2: 1) was separated to obtain a colorless viscous substance (compound Boc-AMP -Gal-Glu) 0.70 g, yield 91%. The hydrogen and carbon spectra of Boc-AMP-Gal-Glu are shown in Figure 11 and Figure 12, respectively.
  • 73
  • [ 19879-84-6 ]
  • C29H44N4O13 [ No CAS ]
  • C42H62N4O22S [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With 2,2-dimethoxy-2-phenylacetophenone; In dichloromethane; at 20℃; for 0.5h;UV-irradiation; Weigh out the compound Boc-AMP-Man-ene (0.68g, 1.04mmol) and beta-D-glucose thiol compound (Glu-SH) (0.45g, 1.24mmol) in 3ml of dichloromethane, then weigh benzoin Methyl ether (DMPA) (10.6 mg, 0.04 mmol) was added to the above reaction solution. After stirring and dissolving, the reaction solution was irradiated with 365 nm ultraviolet light for 30 minutes at room temperature, and TLC followed the detection. After the reaction was completed, the organic phase was washed with dichloromethane / water, and the organic phase was dried over anhydrous sodium sulfate. Silica gel powder was added and the mixture was directly spin-dried. The silica gel column chromatography (developing solvent: PE / EA (v / v) = 1: 1, Eluent: PE / EA (v / v) = 2: 1). 0.88 g of colorless viscous substance (compound Boc-AMP-Man-Glu) was obtained with a yield of 84%. Proton and carbon spectra of Boc-AMP-Man-Glu are shown in Figure 19 and Figure 20, respectively
  • 74
  • [ 19879-84-6 ]
  • [ 10485-09-3 ]
  • [ 1467023-93-3 ]
  • 75
  • [ 75-15-0 ]
  • [ 91-21-4 ]
  • [ 19879-84-6 ]
  • 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl (1,2,3,4-tetrahydroisoquinoline)-2-carbo(dithioperoxo)thioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With N-iodo-succinimide; In dichloromethane; at -45℃; for 0.25h; General procedure: To a mixture of piperidine (2a) (0.1 mL, 1.1 mmol) and CS2 (0.07 mL,1.1 mmol) in CH2Cl2 (5 mL) was added 2,3,4,6-tetra-O-acetyl--D-glucopyranosylthiol (1a) (364 mg,1.0 mmol). The reaction mixture wascooled to -45 C, NIS (248 mg, 1.1 mmol) was added and the resultingmixture was allowed to stir at the same temperature for 15 min. Themixture was diluted with CH2Cl2 (50 mL) and the organic layer wassuccessively washed with 5% Na2S2O3 solution (30 mL), sat. NaHCO3(30 mL) and H2O (30 mL). The organic layer was separated, dried overNa2SO4, filtered and evaporated to dryness. The crude product waspurified over SiO2 using hexane/EtOAc (3:1) as eluent to give purecompound 3a.
  • 76
  • [ 110-89-4 ]
  • [ 75-15-0 ]
  • [ 19879-84-6 ]
  • 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl piperidine-1-carbo(dithioperoxo)thioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With N-iodo-succinimide; In dichloromethane; at -45℃; for 0.25h; General procedure: To a mixture of piperidine (2a) (0.1 mL, 1.1 mmol) and CS2 (0.07 mL,1.1 mmol) in CH2Cl2 (5 mL) was added 2,3,4,6-tetra-O-acetyl--D-glucopyranosylthiol (1a) (364 mg,1.0 mmol). The reaction mixture wascooled to -45 C, NIS (248 mg, 1.1 mmol) was added and the resultingmixture was allowed to stir at the same temperature for 15 min. Themixture was diluted with CH2Cl2 (50 mL) and the organic layer wassuccessively washed with 5% Na2S2O3 solution (30 mL), sat. NaHCO3(30 mL) and H2O (30 mL). The organic layer was separated, dried overNa2SO4, filtered and evaporated to dryness. The crude product waspurified over SiO2 using hexane/EtOAc (3:1) as eluent to give purecompound 3a. Yield: 196 mg (75%); yellow oil; []D25 +48 (c 1.0, CHCl3).IR (neat): 1490 (NC=S), 1280 (C-N), 1100 (C=S) cm-1.1H NMR (500 MHz, CDCl3): = 5.22 (t, J = 9.0 Hz, 1 H, H-3), 5.12-5.07(m, 2 H, H-2, H-4), 4.65 (d, J = 10.0 Hz, 1 H, H-1), 4.28-3.96 (m, 6 H, 2NCH2, H-6a, H-6b) 3.68 (m, 1 H, H-5), 2.15 (s, 3 H, COCH3), 2.09 (s, 3 H,COCH3), 2.02 (s, 6 H, 2 COCH3), 1.75 (s, 6 H, 3 CH2).13C NMR (125 MHz, CDCl3): = 193.8 (C=S), 170.4 (COCH3), 169.8(COCH3), 169.6 (COCH3), 169.2 (COCH3), 88.0 (C-1), 75.9 (C-5), 73.7 (C-3), 69.7 (C-4), 68.0 (C-2), 61.7 (C-6), 58.2 (NCH2), 54.5 (NCH2), 24.2 (3CH2), 20.9 (COCH3), 20.7 (COCH3), 20.6 (COCH3), 20.5 (COCH3).HRMS (ESI): m/z [M + Na]+ calcd for C20H29NO9S3Na: 546.0902; found:546.0912.
  • 77
  • [ 123-75-1 ]
  • [ 75-15-0 ]
  • [ 19879-84-6 ]
  • 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl pyrrolidine-1-carbo(dithioperoxo)thioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With N-iodo-succinimide; In dichloromethane; at -45℃; for 0.25h; General procedure: To a mixture of piperidine (2a) (0.1 mL, 1.1 mmol) and CS2 (0.07 mL,1.1 mmol) in CH2Cl2 (5 mL) was added 2,3,4,6-tetra-O-acetyl--D-glucopyranosylthiol (1a) (364 mg,1.0 mmol). The reaction mixture wascooled to -45 C, NIS (248 mg, 1.1 mmol) was added and the resultingmixture was allowed to stir at the same temperature for 15 min. Themixture was diluted with CH2Cl2 (50 mL) and the organic layer wassuccessively washed with 5% Na2S2O3 solution (30 mL), sat. NaHCO3(30 mL) and H2O (30 mL). The organic layer was separated, dried overNa2SO4, filtered and evaporated to dryness. The crude product waspurified over SiO2 using hexane/EtOAc (3:1) as eluent to give purecompound 3a.
  • 78
  • [ 110-91-8 ]
  • [ 75-15-0 ]
  • [ 19879-84-6 ]
  • 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl morpholine-1-carbo(dithioperoxo)thioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With N-iodo-succinimide; In dichloromethane; at -45℃; for 0.25h; General procedure: To a mixture of piperidine (2a) (0.1 mL, 1.1 mmol) and CS2 (0.07 mL,1.1 mmol) in CH2Cl2 (5 mL) was added 2,3,4,6-tetra-O-acetyl--D-glucopyranosylthiol (1a) (364 mg,1.0 mmol). The reaction mixture wascooled to -45 C, NIS (248 mg, 1.1 mmol) was added and the resultingmixture was allowed to stir at the same temperature for 15 min. Themixture was diluted with CH2Cl2 (50 mL) and the organic layer wassuccessively washed with 5% Na2S2O3 solution (30 mL), sat. NaHCO3(30 mL) and H2O (30 mL). The organic layer was separated, dried overNa2SO4, filtered and evaporated to dryness. The crude product waspurified over SiO2 using hexane/EtOAc (3:1) as eluent to give purecompound 3a.
  • 79
  • [ 75-15-0 ]
  • [ 31252-42-3 ]
  • [ 19879-84-6 ]
  • 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl 4-benzylpiperidine-1-carbo(dithioperoxo)thioate [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With N-iodo-succinimide; In dichloromethane; at -45℃; for 0.25h; General procedure: To a mixture of piperidine (2a) (0.1 mL, 1.1 mmol) and CS2 (0.07 mL,1.1 mmol) in CH2Cl2 (5 mL) was added 2,3,4,6-tetra-O-acetyl--D-glucopyranosylthiol (1a) (364 mg,1.0 mmol). The reaction mixture wascooled to -45 C, NIS (248 mg, 1.1 mmol) was added and the resultingmixture was allowed to stir at the same temperature for 15 min. Themixture was diluted with CH2Cl2 (50 mL) and the organic layer wassuccessively washed with 5% Na2S2O3 solution (30 mL), sat. NaHCO3(30 mL) and H2O (30 mL). The organic layer was separated, dried overNa2SO4, filtered and evaporated to dryness. The crude product waspurified over SiO2 using hexane/EtOAc (3:1) as eluent to give purecompound 3a.
  • 80
  • [ 19879-84-6 ]
  • [ 134457-14-0 ]
  • [ 1033694-65-3 ]
  • 81
  • [ CAS Unavailable ]
  • [ 19879-84-6 ]
  • [ 554-70-1 ]
  • [ 34031-32-8 ]
YieldReaction ConditionsOperation in experiment
72% Stage #1: potassium tetrachloroaurate(III) With 4,4'-Thiodiphenol In water; acetone at 0 - 20℃; Stage #2: triethylphosphine In water; acetone at 0℃; for 3h; Stage #3: tetraacetyl thioglucose With potassium carbonate In dichloromethane; water; acetone at 20℃; for 2h; 10 Potassium chloroaurate (906mg, 2.4mmol) was dissolved in a mixed solvent of water:acetone=4:1 (20mL), the temperature of the reaction solution was reduced to 0, and 4-4'-dihydroxydiphenyl sulfide (1.05 g, 4.8mmol),After stirring and mixing uniformly, add triethylphosphine (323μL, 2.4mmol), react at a constant temperature of 0°C for 3 hours, then addTetraacetylglucose 1-thiol(878mg, 2.4mmol)React with potassium carbonate (400mg, 2.9mmol) for 2 hours.The crude reaction product obtained is obtained after extraction and purificationZinofin1.17 grams of pure product,The yield was 72%.
  • 82
  • [ 19879-84-6 ]
  • [ 15529-90-5 ]
  • [ 34031-29-3 ]
  • 83
  • [ 19879-84-6 ]
  • [ 55628-54-1 ]
  • 3,4,6-tri-O-benzyl-2-deoxy-α-D-glucopyranosyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With [ReOCl3(OPPh3)(SMe2)] In toluene at 0 - 20℃; for 5h; Inert atmosphere; 4.2 General procedure for rhenium catalyzed thioglycosylation in Scheme 2 General procedure: A solution of glycal (50mg, 1.0 equiv) and glycosyl thiol (1.2 equiv) in toluene (0.4M) was stirred at 0°C under Ar atmosphere. Then [ReOCl3(SMe2)(OPPh3)] (1 or 10mol %) was added. The reaction was stirred at 0°C for 10min and then warmed up to room temperature. Upon complete consumption of the starting materials, the crude reaction mixture was loaded directly onto a silica gel column and purified by chromatography (eluting with petroleum ether/ethyl acetate).
  • 84
  • [ 19879-84-6 ]
  • [ 34301-54-7 ]
  • C24H34O9S4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% Stage #1: 1-Adamantanethiol With 5,10-dihydro-6,9-dioxa-7,8-dithia-benzocyclooctene In methanol at -78℃; for 0.5h; Stage #2: tetraacetyl thioglucose With tris(pentafluorophenyl)borate In dichloromethane for 4h; 70 Synthesis of compound 4g: At -78, add adamantane mercaptan (16.8mg, 0.1mmol) in methanol (1mL) solution dropwise to the methanol (1mL) solution of 6 (24.0mg, 0.12mmol, 1.2equiv), and react for 0.5 hours to remove the methanol , Add glucosinolate (40.0mg, 0.11mmol, 1.1equiv), B(C6F5)3 (1.0mg, 0.001mmol, 2mol%) and dichloromethane (1mL), react for four hours, remove the solvent, and column chromatography gives white Solid 4g (33.8mg, 57%).
  • 85
  • [ 19879-84-6 ]
  • [ 108-24-7 ]
  • [ 2106-10-7 ]
  • [ 5505-45-3 ]
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