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CAS No. : | 2873-29-2 | MDL No. : | MFCD00063253 |
Formula : | C12H16O7 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LLPWGHLVUPBSLP-UTUOFQBUSA-N |
M.W : | 272.25 | Pubchem ID : | 688303 |
Synonyms : |
|
Num. heavy atoms : | 19 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.58 |
Num. rotatable bonds : | 7 |
Num. H-bond acceptors : | 7.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 62.15 |
TPSA : | 88.13 Ų |
GI absorption : | High |
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) : | -7.84 cm/s |
Log Po/w (iLOGP) : | 2.17 |
Log Po/w (XLOGP3) : | 0.17 |
Log Po/w (WLOGP) : | 0.33 |
Log Po/w (MLOGP) : | -0.08 |
Log Po/w (SILICOS-IT) : | 0.29 |
Consensus Log Po/w : | 0.57 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.17 |
Solubility : | 18.3 mg/ml ; 0.0671 mol/l |
Class : | Very soluble |
Log S (Ali) : | -1.58 |
Solubility : | 7.19 mg/ml ; 0.0264 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -0.48 |
Solubility : | 89.5 mg/ml ; 0.329 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 0.0 |
Synthetic accessibility : | 4.32 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With boron trifluoride diethyl etherate In acetonitrile for 0.166667h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With indium(III) chloride; indium; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran; water at 20℃; for 8h; | |
95% | With bis(cyclopentadienyl)-titanium(III) chloride In tetrahydrofuran Ambient temperature; | |
94% | With bis(cyclopentadienyl)-titanium(III) chloride In tetrahydrofuran for 0.25h; Ambient temperature; |
92% | With β‐cyclodextrin; zinc In water at 20℃; for 0.5h; Sonication; | |
87% | In tetrahydrofuran at 20℃; | |
86% | With manganese; chloro-trimethyl-silane In tetrahydrofuran at 20℃; for 12h; | |
85% | With ammonium chloride; zinc In acetonitrile at 60℃; for 0.416667h; Inert atmosphere; | 2. General procedure for the synthesis of glycals General procedure: Under nitrogen, the glycopyranosyl bromide (1.0 mmol) was dissolved in CH3CN, and then zinc dust (7.5 mmol) and ammonium chloride (7.5 mmol) were added, followed by stirring at corresponding temperature. Upon completion of the reaction (monitored by TLC), inorganic salts and excessive zinc dust were removed by filtration. The filtrate was concentrated in vacuo and the residue was purified by silica gel flash column chromatography to afford the corresponding glycal in pure form. |
84% | With lithium perchlorate In tetrahydrofuran Electrochemical reaction; | |
83% | With sodium dihydrogenphosphate; zinc In acetone at 20℃; for 5h; | |
81% | With zinc In water at 20℃; for 1h; | |
78% | With aluminium amalgam In tetrahydrofuran; water for 5h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With stannic bromide; In dichloromethane; at 0℃; for 0.5h; | Tri-O-acetyl-D-glucal (1; 3.0 g, 11 mmol) and Cbz-Ser-OBn (3, 3.63 g,11 mmol) dissolved in anhydrous dichloromethane (60 mL) were treated dropwise at 0 C with a solution of tin tetrabromide in anhydrous dichloromethane (11 mL,1 M) for 30 min under stirring. The mixture was neutralized with a saturated aqueous solution of sodium hydrogen carbonate, the organic phase separated, dried (MgSO4), filtered, evaporated and the raw material purified by column chromatography (n-hexane/ether 1:1) to give5.95 g (99%) of 4 as a colorless sirup; [a]20D=+18.3 (c1.0, CHCl3).1H-NMR (250 MHz, C6D6): d4.57 (d, 1H, J1,2 2.4 Hz, H-1), 5.32 (dd,1H, J1,2 2.4, J2,3 10.0 Hz, H-2), 5.68 (dd, 1H, J2,3 10.0, J3,4 1.2 Hz,H-3), 5.38 (dd, 1H, J3,4 1.2, J4,5 9.5 Hz, H-4), 4.06 (m, 1 H, H-5), 4.20(dd, 1H, J5,6a 5.2, J6a,6b 12.1 Hz, H-6a), 4.32 (dd, 1H, J5,6b 2.4, J6a,6b 12.1 Hz, H-6b), 4.65 (mc, 1H,CHa-Ser), 3.82 (mc, 2H, CHb-Ser), 6.08(d, 1H, JNH,CHa-Ser 8.5 Hz, NH-Ser), 4.86, 5.03 (2d, 2H, CH2-Ph), 5.08 (s,2H, CH2-Ph), 1.65, 1.72 (2 s, 6H, OAc), 7.20 (m, 10H, aryl-H). Calcd. for C28H31NO10 (541.4): C, 62.10; H, 5.77; N, 2.59. Found: C, 62.00; H, 5.80;N, 2.70. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With magnesium oxide In chlorobenzene at -10 - 23℃; for 8h; | |
91% | With tetrakis(μ-trifluoroacetamidato)dirhodium(II); magnesium oxide In chlorobenzene at 5 - 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With niobium pentachloride In dichloromethane at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene at 20℃; for 0.75h; | 7.d d) Preparation of [1R-(2R, 3S, 6S)]-3-acetoxy-6-(2-phenylpropoxy)-3,6-dihydro-2H- pyran-2-methanol acetate, [1R-(2R, 3S, 6R)]-3-acetoxy-6-(2-phenylpropoxy)-3, 6- dihydro-2H-pyran-2-methanol acetate, [1S-(2R, 3S, 6S)]-3-acetoxy-6-(2-phenylpropoxy)- 3, 6-dillydro-2H-pyran-2-methanol acetate and [IS-(2R, 3S, 6R) 1-3-acetoxy-6-(2- phenylpropoxy)-3, 6-dihydro-2H-pyran-2-methanol acetate; 2-Phenyl-l-propanol (29.9 mg, 219. 5. mol) was added to a mixture of anhydrous zinc chloride (5.3 mg, 38.9 umol) and 3,4, 6-tri-O-acetyl-D-glucal (59.5 mg, 218. 5 jjmol) under a stream of nitrogen. The solution was stirred for 2.5 h at 50 °C. Spectral analysis of the yellow tinged crude oil (74.8 mg) showed the presence of the expected two pairs of diastereoisomers in a trans/cis ratio of 9: 1, respectively. Attempted separation of the diastereomers using column chromatography or HPLC was unsuccessful. Assignments of the 13C nmr spectrum was possible after reacting optically active (R)-2-phenyl-1-propanol or (S)-2-phenyl-l-propanol with 3,4, 6-tri-O-acetyl-D-glucal. A solution of 3,4, 6-tri-O- acetyl-D-glucal (154.5 mg, 0.57 mmol), (R)-2-phenyl-1-propanol (77.0 mg, 0.57 mmol) in dry benzene (1 ml) was treated with BF3. Et20 (8.0 mg, 56.4 mol). The solution was stirred at ambient temperature for 45 min prior to being quenched with saturated NaHCO3 solution (15 ml). The aqueous layer was extracted with ether (3 x 15 ml). The combined etherel fractions were washed with brine (15 ml), dried with MgS04, filtered and concentrated in vacuo affording a yellow tinged oil (0.23 g). lH and 13C nmr spectroscopic analysis showed largely starting material (81%) with the emergence of the expected products (19%). The trans/cis isomeric ratio was 2: 1, respectively. 13C nmr (75 MHz, CDC13) 8 18. 1 (cis-CH3); 18.2 (trans-CH3) ; 20.6, 20.8 (trans/cis-COCH3), 39.9 (trans/cis- CH) ; 62.8 (trans-CH20Ac); 63.4 (cis-CH20Ac) ; 64.2 (cis-C3); 65.1 (trans-C3) ; 66.8 (trans-C2) ; 72.6 (cis-C2) ; 74.3 (trans/cis-CH20) ; 94.4 (trans-C6); 95.1 (cis-C6) ; 125.7 (cis- C4); 126.3 (trans/cis-C4'); 127.21 (trans-C2'& C6'); 127.25 (cis-C2'& C6'); 127.7 (trans- C4); 128.22 (cis-C3'& C5') ; 128.24 (trans-C3'& C5') ; 128. 9 (trans-C5) ; 130.4 (cis-C5) ; 144.0, 144.1 (trans/cis-Cl') ; 170.1, 170.6 (trans/cis-CO). Using the previously outlined protocol, a solution of (S)-2-phenyl-l-propanol (75.7 mg, 0.55 mmol) and 3,4, 6-tri-O- acetyl-D-glucal (0.16 g, 0.55 mmol) was treated with BF3. Et20 (8.6 mg, 60.6 amol) to afford a yellow tinged oil (0.21 g) after work-up and 13C nmr spectroscopic analysis predominantly showed starting material (67%) with the emergence of the expected products (33%). The trans/cis isomeric ratio was 2: 1, respectively. 13C nmr (75 MHz, CDC13) 8 18. 1 (cis-CH3); 18. 2 (trans-CH3); 20.6, 20. 8 (trans/cis-COCH3), 39.7 (trans-CH); 39.8 (cis-CH); 62.9 (trans-CH2OAc) ; 63.2 (cis-CH2OAc) ; 65. 1 (trans-C3); 66.9 (trans-C2) ; 72.6 (cis-C2); 73.8 (cis-CH20) ; 74.2 (trans-CH20) ; 94.2 (trans-C6); 95.2 (cis-C6); 125.9 (cis-C4); 126.27 (cis-C4'); 126.31 (trans-C4'); 127.1 (trans-C2'& C6'); 127.2 (cis-C2'& C6'); 127.7 (trans-C4); 128.2 (trans/cis-C3'& C5') ; 128.9 (trans-C5) ; 130.3 (cis-C5) ; 143. 8 (trans/cis-C1') ; 170.1, 170.6 (trans/cis-CO) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With aluminum oxide; zinc(II) chloride for 0.25h; stereoselective reaction; | |
80% | With (1S)-10-camphorsulfonic acid In dichloromethane at 20℃; for 3h; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With zinc dibromide; In chloroform; at 72℃; for 0.25h;Microwave irradiation; | General procedure: In a typical reaction (Scheme 1), anhydrous ZnBr2(0.5 mmol) was added to a mixture of 3,4,6- tri-O-acetyl glucal (5 mmol) and a phenol or alcohol (4.5 mmol) in CHCl3(8 mL). A Teflon heating button and a stirring bar were introduced into the flask, which was then equipped with condenser and irradiated with microwave radiation(400 W) under open-vessel conditions in a Milestone START-S microwave labstation at 72C for a specified time period (Tables 1-5). After the completion of the reaction, water (15 ml) was added to the reaction mixture and the organic layer was separated. The aqueous layer was extracted with chloroform (25 ml). The combined organic layers was dried over anhydrous Na2SO4 and concentrated to afforda syrupy crude mass, which was refined by column chromatography on silica gel(100-200 mesh) using ethyl acetate (5-10%) in petroleum ether (60-80 C) as the eluent.The ratio of alpha and beta anomers, which had close Rf values and eluted together, was determined by integration of the corresponding hydrogen signals in the 1HNMR of the crude product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
12% | With boron trifluoride diethyl etherate; at 0℃; for 1.0h;Inert atmosphere; | Synthesis Example 5-4: Preparation of SAC-0902; Magnesium turning (Aldrich, 92 mg) was dissolved in tetrahydrofuran (3 mL) under argon flow and, after adding catalytic amount of iodine, 1-bromo-4-methylpentane (Aldrich, 0.69 mL) was slowly added. When the magnesium turning disappeared, pregnenolone (Aldrich, 200 mg) dissolved in tetrahydrofuran (4 mL) was slowly added. 10 minutes later, reaction was stopped by adding 2 N hydrochloric acid solution and the reaction mixture was extracted with ethyl acetate (20 mL), dried with magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure and the residue was subjected to silica gel column chromatography using ethyl acetate/hexane (1:10) as eluent to obtain the compound 3 (95 mg, 15%), which is commercially available (Fluka H6378). The compound 3 (43 mg) was dissolved in diethyl ether (5 mL). After adding tri-O-acetyl-D-glucal (Aldrich, 81 mg) and boron trifluoride diethyl etherate (Aldrich, 0.012 mL) under argon flow, the mixture was stirred at 0 C for 1 hour. The reaction mixture was diluted by adding diethyl ether (30 mL), washed with aqueous sodium bicarbonate solution, dried with sodium sulfate, and then filtered. The filtrate was concentrated under reduced pressure and the residue was subjected to silica gel column chromatography using ethyl acetate/hexane (1:10) as eluent to obtain the target compound SAC-0902 (7.6 mg, 12%): 1H-NMR (500 MHz, CDCl3) delta 5.86 (d, 1H, J = 10.2 Hz), 5.81 (d, 1H, J = 10.2 Hz), 5.38 (m. 1H), 5.27 (m, 1H), 5.14 (m, 1H), 4.23-4.09 (m, 3H), 3.55 (m, 1H), 2.41-2.32 (m, 2H), 2.07-2.06 (m, 7H), 2.14-0.52 (m, 38H). |
12% | With boron trifluoride diethyl etherate; In diethyl ether; at 0 - 20℃; for 1.0h; | To a solution of 11 (Fluka, H6378)(43 mg, 0.11 mmol) with tri-O-acetyl-D-glucal (81 mg, 0.30 mmol)in diethylether (5 mL) was added boron trifluoride diethyl etherate (0.012 mL, 0.10 mmol) at 0 C. The reaction mixture was stirred for1 h at ambient temperature. The reaction mixture was quenchedwith saturated aqueous NaHCO3 and diluted with EtOAc. Theorganic phase was washed with H2O and brine, dried over MgSO4,and concentrated in vacuo. Purification of the residue via flashcolumn chromatography on silica gel (EtOAc:n-Hexane 1:10)afforded 7.6 mg (12%) of 6: 1H NMR (CDCl3, 500 MHz) d 5.87e5.79(dd, J 27.1, 10.2 Hz, 2H), 5.38 (m, 1H), 5.27 (m, 1H), 5.16 (s, 1H),4.24e4.09 (m, 3H), 3.55 (m, 1H), 2.41-0.76 (m, 47H), 0.69 (d, 1H,J 6.75 Hz), 0.54(m, 1H). The mass spectral data of analog 6 givesthe same value of analog 8, because of dehydration. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tellurium tetrachloride; In dichloromethane; at 20℃; for 0.05h;Inert atmosphere; | General procedure: To a 50 mL round bottomed flask containing a solution of 1 (272 mg, 1.0 mmol) and appropriate alcohol (1.2 mmol) in dichloromethane (10 mL) at 0 C under argon was added TeCl4 (5 mg, 2 mol %). The ice bath was removed and the mixture was stirred for the time indicated in Tables 2 and 6. A saturated solution of ammonium chloride (5 mL) was then added and the mixture was extracted with EtOAc (2×10 mL). The combined organic phases were dried over MgSO4 and the solvents were removed under reduced pressure followed by purification by a flash column chromatography [hexanes/EtOAc (95:5)] to yield the corresponding 2,3-unsaturated O-glycopyranosides. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tellurium tetrachloride; In dichloromethane; at 20℃; for 0.333333h;Inert atmosphere; | General procedure: To a 50 mL round bottomed flask containing a solution of 1 (272 mg, 1.0 mmol) and appropriate alcohol (1.2 mmol) in dichloromethane (10 mL) at 0 C under argon was added TeCl4 (5 mg, 2 mol %). The ice bath was removed and the mixture was stirred for the time indicated in Tables 2 and 6. A saturated solution of ammonium chloride (5 mL) was then added and the mixture was extracted with EtOAc (2×10 mL). The combined organic phases were dried over MgSO4 and the solvents were removed under reduced pressure followed by purification by a flash column chromatography [hexanes/EtOAc (95:5)] to yield the corresponding 2,3-unsaturated O-glycopyranosides. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tellurium tetrachloride; In dichloromethane; at 0 - 20℃; for 0.333333h;Inert atmosphere; | General procedure: To a 50 mL round bottomed flask containing a solution of 1 (272 mg, 1.0 mmol) and appropriate alcohol (1.2 mmol) in dichloromethane (10 mL) at 0 C under argon was added TeCl4 (5 mg, 2 mol %). The ice bath was removed and the mixture was stirred for the time indicated in Tables 2 and 6. A saturated solution of ammonium chloride (5 mL) was then added and the mixture was extracted with EtOAc (2×10 mL). The combined organic phases were dried over MgSO4 and the solvents were removed under reduced pressure followed by purification by a flash column chromatography [hexanes/EtOAc (95:5)] to yield the corresponding 2,3-unsaturated O-glycopyranosides. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 61% 2: 13% | With iron(III) chloride; bis(3,5-bis(trifluoromethyl)phenyl)(2’,4’,6’-triisopropyl-3,6-dimethoxy-[1,1’-biphenyl]-2-yl)phosphine In tetrahydrofuran at 20℃; for 1h; diastereoselective reaction; | |
1: 30% 2: 12% | With iron(II) acetate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In tetrahydrofuran at 20℃; for 1h; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With iron(III) chloride; para-fluorostyrene In tetrahydrofuran at 0 - 20℃; for 1h; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(II) bis(trifluoromethanesulfonate); In acetonitrile; at 20℃; for 1h;Inert atmosphere; Sealed tube; Green chemistry; | General procedure: To a stirred solution of3,4,6-tri-O-acetyl-D-glucal 1 (1 equiv) and acceptor (1.2 equiv) in anhydrous acetonitrile (2mL/mmol) under an atmosphere of argon was added Cu(OTf)2 (2 mol%) at room temperature.The reaction mixture was stirred until the complete consumption of the starting material (glycal).The solvent was concentrated in vacuo, the crude residue was re-dissolved in dichloromethaneand loaded on a silica gel column. The product was purified by silica gel chromatography usingHexane/EtOAc to afford the 2,3-unsaturated-O-glycosides in excellent yields. All the Ferrierproducts were confirmed by IR, 1H NMR, 13C NMR and MS/HRMS spectroscopy. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50 % de | With trichloro(trifluoromethanesulfonato)titanium(IV) In dichloromethane at 40℃; for 0.333333h; Overall yield = 83 %; | 12 General procedure for preparation of 2,3-unsaturated glycosides General procedure: To a stirred solution of tri-O-acetyl-d-glucal (188 mg, 0.7 mmol) and the corresponding alcohol (1.3 equiv) in DCM (5 mL) were added TiCl3(OTf) (10 mol %) at ambient temperature. The mixture was stirred under 40 °C for the appropriate amount of time (Table 3), and the extent of the reaction was monitored by TLC analysis. The reaction mixture was diluted with cooled sodium bicarbonate (satd, 20 mL) and extracted with DCM (3×10 mL). The combined organics were dried over anhydrous Na2SO4. The solvent was removed under vacuum. All the products were purified by silica gel column chromatography (hexane/EtOAc=6/1). |
50 % de | With triflic acid supported on silica gel at 40℃; for 0.416667h; Overall yield = 67 %; | 12 General procedure for preparation of 2,3-unsaturated glycosides General procedure: To a stirred solution of tri-O-acetyl-D-glucal(136mg, 0.5 mmol) and the corresponding alcohol (1.2 eq) in THF (8 mL) were added CF3SO3H-SiO2 (10mol%) at ambient temperature.The mixture was stirred under 40°C for the appropriate amount of time (Table 3), and the extent of the reaction was monitored by TLC analysis.The reaction mixture was diluted with cooled sodium bicarbonate (sat., 20 mL)and extracted with DCM ( 3 X 10 mL). The combined organics were dried overanhydrous Na2SO4.The solvent was removed under vacuum. All the products were purified by silica gel column chromatography (hexane /EtOAc=6 / 1). 4.2.12 2,2,2-Trifluoro-1-phenyl ethyl 4,6-di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (3l) Colorless oil; [α]25D[α]D25 +61 (c 0.58, CHCl3, α:β=3:1); 1H NMR (400 MHz, CDCl3): δ α-anomer: 2.13 (s, 6H), 4.24-4.32 (m, 3H), 4.93 (s, 1H), 5.11 (dd, J=12.8, 6.2 Hz, 1H), 5.28-5.37 (m, 1H), 5.81 (d, J=9.9 Hz, 1H), 5.98 (d, J=10.8 Hz, 1H), 7.35-7.55 (m, 5H) ppm; β-anomer: 1.91 (s, 1H), 2.06 (s, 1H), 3.49 (d, J=12.2 Hz, 0.3H), 3.72 (d, J=8.4 Hz, 0.3H), 3.93 (d, J=12.3 Hz, 0.3H), 4.99 (d, J=6.5 Hz, 0.3H), 5.01 (d, J=6.5 Hz, 0.3H), 5.39 (s, 0.3H). 13C NMR (101 MHz, CDCl3): δ α-anomer: 20.66, 20.91, 62.67, 65.05, 67.77, 75.77, 77.71, 91.71,126.52, 128.51, 128.72, 129.84, 130.48, 131.91, 170.25, 170.70; β-anomer: 20.54, 20.58, 61.87, 64.82, 67.42, 75.77, 78.02, 96.12, 126.44, 127.74, 128.44, 129.28, 130.34, 133.69, 170.08, 170.53; 19F NMR (282 MHz, CDCl3): δ -76.34 (d, J=6.7 Hz), -76.69 (d, J=6.6 Hz) ppm; IR (film, cm-1): 2966, 2361, 1745, 1448, 1374, 1234, 1175, 1045, 988, 910, 759, 705, 608; MS (ESI) m/z: 406.1 ([M+NH4]+, 100); 213.1 (30); HR-ESI C18H19O6F3Na1 [M+Na]+ calcd 411.10408,found 411.10259. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With palladium diacetate; In acetonitrile; at 20℃; | Prepared from (2R,3S,4R)-3,4-diacetoxy-3,4-dihydro-2H-pyran-2-yl]methyl acetate (1.49 g, 5.47 mmol) and <strong>[173194-95-1](6-hydroxy-2-naphthyl)boronic acid</strong> (l.Og, 5.32 mmol) following the same procedure than INTERMEDIATE A, step I. Purification by flash chromatography on Biotage snap 50g cartridge using a gradient of EtOAc in hexanes (0-50%) affords the title compound an off-white foamy solid (935 mg, 49% yield). |
49% | With palladium diacetate; In acetonitrile; at 20℃;Inert atmosphere; | Step I: [(2R,3 S,6S)-3-Acetoxy-6-(6-hydroxy-2-naphthyl)-3,6-dihydro-2H-pyran-2-yl]methyl acetate Acetonitrile (10 mL) is added to a mixture of [(2R,3S,4R)-3,4-diacetoxy-3,4-dihydro- 2H-pyran-2-yl]methyl acetate (1.49 g, 5.47 mmol), <strong>[173194-95-1](6-hydroxy-2-naphthyl)boronic acid</strong> (1.0 g, 5.32 mmol) and diacetoxypalladium (119 mg, 0.53 mmol). The reaction mixture is stirred overnight at RT under N2, then filtered through silica cartridge (5 g), and rinsed with EtOAc. Combined filtrates are concentrated, and purified on Biotage SNAP 50 g silica gel cartridge using a gradient of EtOAc in Hex (0-50%). Pure fractions are combined and concentrated to provide title compound (935 mg, 2.62 mmol, 49% yield) as an off-white foamy solid. XH NMR (400 MHz, CDC13) delta 7.80 - 7.72 (m, 2H), 7.70 (d, J= 8.5 Hz, 1H), 7.51 (dd, J= 8.5, 1.7 Hz, 1H), 7.18 - 7.08 (m, 2H), 6.28 (ddd, J= 10.4, 3.1, 1.6 Hz, 1H), 6.13 - 6.00 (m, 1H), 5.49 - 5.42 (m, 1H), 5.36 (ddd, J= 7.4, 4.1, 2.1 Hz, 1H), 4.28 (dd, J= 12.0, 5.8 Hz, 1H), 4.09 (dd, J= 12.0, 3.0 Hz, 1H), 3.86 (ddd, J= 7.8, 5.8, 3.0 Hz, 1H), 2.10 (s, 3H), 2.08 (s, 3H). LC-MS:m/z = 357.34 (M+ H +). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28% | With palladium diacetate; In acetonitrile; at 20℃; for 50.0h; | To a solution of [(2R,3S,4R)-3,4-diacetoxy-3,4-dihydro-2H-pyran-2-yl]methyl acetate (0.900 g, 3.31 mmol in lOmL of CCN are added (4-chloro-3-hydroxy-phenyl)boronic acid (1.140 g, 6.61 mmol) and Pd(OAc)2 (111 mg, 0.496 mmol). The mixture was stirred at room temperature for 23h.To the reaction was added another portion of Pd(OAc)2 (111 mg, 0.496 mmol) and (4-chloro-3-hydroxy-pheny)boronic acid (0.350 g, 2.03 mmol). It was then stirred at room temperature for 27h, when complete consumption of the starting material was observed. The mixture was diluted with 10 mL of CH2CI2 and filtered over a pad of celite. The filtrate was concentrated to a black foam (1.50 g). The crude material was purified on a 50g SNAP silica cartridge, eluting with Hex/EtOAc (0-50%) to give the title compound (328 mg, 28%) as a white foam. LC-MS: m/z = 363 (M+Na+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With palladium diacetate; In acetonitrile; at 20℃; | To a solution of [(2R,3S,4R)-3,4-diacetoxy-3,4-dihydro-2H-pyran-2-yl]methyl acetate (1.100 g, 4.040 mmol) in 10 mL of acetonitrile are added [3-(tert-butyl-dimethyl- silyl)oxyphenyl]boronic acid (2.038 g, 8.080 mmol) and Pd(OAc)2 (136.1 mg, 0.6060 mmol). The mixture is stirred at rt for 5 h and then to it are added another batch of Pd(OAc)2 (136 mg, 0.606 mmol) and [3-(tert-butyl-dimethyl-silyl)oxyphenyl]boronic acid (2.038 g, 8.080 mmol). It is then stirred at rt overnight. The mixture is diluted with 20 mL of CH2CI2 and filtered over a pad of celite. The filtrate is concentrated and the residue is separated on Biotage SNAP lOOg silica gel cartridge using a gradient of Hex/EtOAc (0-20%) in 20 column volume to afford the title compound (805 mg, 1.91 mmol, 47%) as an oil, which solidifies upon standing. XH NMR (CDCI3, 400 MHz): 7.06 (m, 1H), 6.78 (m, 1H), 6.70 (m, 1H), 6.60 (m, 1H), 5.97 (m, 1H), 5.71 (m, 1H), 5.09 (m, 2H), 4.08 (m, 1H), 3.85 (m, 1H), 3.62 (m, 1H), 1.88 and 1.87 (2s, 6H), 0.78 (m, 9H), 0.00 (m, 6H). |
47% | With palladium diacetate; In acetonitrile; at 20℃; | Step I: [(2R,3S,6S)-3-Acetoxy-6-[3-[ter/-butyl(dimethyl)silyl]oxyphenyl]-3,6-dihydro-2H- pyran-2-yl]methyl acetate To a solution of [(2R,3S,4R)-3,4-diacetoxy-3,4-dihydro-2H-pyran-2-yl]methyl acetate (1.100 g, 4.040 mmol) in 10 mL of CH3CN are added [3-(tert-butyl-dimethyl- silyl)oxyphenyl]boronic acid (2.038 g, 8.080 mmol) and Pd(OAc)2 (136.1 mg, 0.6060 mmol). The mixture is stirred at RT for 5 h and then to it are added another batch of Pd(OAc)2 (136 mg, 0.606 mmol) and [3-(/er/-butyl-dimethyl-silyl)oxyphenyl]boronic acid (2.038 g, 8.080 mmol). It is then stirred at RT overnight. The mixture is diluted with 20 mL of CH2CI2 and filtered over a pad of celite. The filtrate is concentrated and the residue is separated on Biotage SNAP lOOg silica gel cartridge using a gradient of EtO Ac in Hex (0-20%) in 20 column volume to afford the title product (805 mg, 47%) as an oil, which solidifies upon standing. XH NMR (CDC13, 400 MHz): 7.06 (m, 1H), 6.78 (m, 1H), 6.70 (m, 1H), 6.60 (m, 1H), 5.97 (m, 1H), 5.71 (m, 1H), 5.09 (m, 2H), 4.08 (m, 1H), 3.85 (m, 1H), 3.62 (m, 1H), 1.88 and 1.87 (2s, 6H), 0.78 (m, 9H), 0.00 (m, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 20℃; for 2h; Inert atmosphere; Sealed tube; Green chemistry; stereoselective reaction; | General procedure for the Cu(OTf)2-catalyzed Ferrier glycosylation General procedure: To a stirred solution of3,4,6-tri-O-acetyl-D-glucal 1 (1 equiv) and acceptor (1.2 equiv) in anhydrous acetonitrile (2mL/mmol) under an atmosphere of argon was added Cu(OTf)2 (2 mol%) at room temperature.The reaction mixture was stirred until the complete consumption of the starting material (glycal).The solvent was concentrated in vacuo, the crude residue was re-dissolved in dichloromethaneand loaded on a silica gel column. The product was purified by silica gel chromatography usingHexane/EtOAc to afford the 2,3-unsaturated-O-glycosides in excellent yields. All the Ferrierproducts were confirmed by IR, 1H NMR, 13C NMR and MS/HRMS spectroscopy. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72 % de | With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 20℃; for 12h; Inert atmosphere; Sealed tube; Green chemistry; Overall yield = 62 %; stereoselective reaction; | General procedure for the Cu(OTf)2-catalyzed Ferrier glycosylation General procedure: To a stirred solution of3,4,6-tri-O-acetyl-D-glucal 1 (1 equiv) and acceptor (1.2 equiv) in anhydrous acetonitrile (2mL/mmol) under an atmosphere of argon was added Cu(OTf)2 (2 mol%) at room temperature.The reaction mixture was stirred until the complete consumption of the starting material (glycal).The solvent was concentrated in vacuo, the crude residue was re-dissolved in dichloromethaneand loaded on a silica gel column. The product was purified by silica gel chromatography usingHexane/EtOAc to afford the 2,3-unsaturated-O-glycosides in excellent yields. All the Ferrierproducts were confirmed by IR, 1H NMR, 13C NMR and MS/HRMS spectroscopy. |
80 % de | With dichloro bis(acetonitrile) palladium(II) In dichloromethane at 20℃; for 7h; Sealed tube; Inert atmosphere; Overall yield = 90 %; Overall yield = 89 mg; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(μ-trifluoroacetamidato)dirhodium(II); iodosylbenzene In chlorobenzene at 5 - 20℃; Molecular sieve; Inert atmosphere; stereoselective reaction; | |
75% | Stage #1: 2-phenylethanol; 2,2,2-trichloroethyl sulfamate; D-glucal triacetate With tetrakis(μ-trifluoroacetamidato)dirhodium(II) In chlorobenzene Molecular sieve; Inert atmosphere; Stage #2: With iodosylbenzene In chlorobenzene at 5 - 20℃; Molecular sieve; Inert atmosphere; stereoselective reaction; | General procedure for one-pot amidoglycosylation General procedure: To a mixture of glycal 1a,b,c (0.2 mmol), alcohol (0.4 mmol),TcesNH2 (80 mg, 0.35 mmol), Rh2(NHCOCF3)4 (12 mg, 0.02 mmol),and activated powdered molecular sieves 4 Å (160 mg) under nitrogen was added PhCl (3 mL), and the resulting light-purple suspension was cooled with an ice-water bath. PhIO (80 mg,0.36 mmol) was added in several portions for 1 h, and the resulting light-brown suspension was stirred at 5°C for 1 h and then at rt for 5-15 h with monitoring the reaction by TLC. The reaction mixture was filtered, washed with CH2Cl2, and the combined filtrates were concentrated under reduced pressure to remove CH2Cl2. The residue was purified by silica gel chromatography, usually eluting with hexane-EtOAc mixture |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With tetrakis(μ-trifluoroacetamidato)dirhodium(II); iodosylbenzene In chlorobenzene at 5 - 20℃; Molecular sieve; Inert atmosphere; stereoselective reaction; | |
57% | Stage #1: 2,2,2-trichloroethyl sulfamate; cyclohexanol; D-glucal triacetate With tetrakis(μ-trifluoroacetamidato)dirhodium(II) In chlorobenzene Molecular sieve; Inert atmosphere; Stage #2: With iodosylbenzene In chlorobenzene at 5 - 20℃; Molecular sieve; Inert atmosphere; stereoselective reaction; | General procedure for one-pot amidoglycosylation General procedure: To a mixture of glycal 1a,b,c (0.2 mmol), alcohol (0.4 mmol),TcesNH2 (80 mg, 0.35 mmol), Rh2(NHCOCF3)4 (12 mg, 0.02 mmol),and activated powdered molecular sieves 4 Å (160 mg) under nitrogen was added PhCl (3 mL), and the resulting light-purple suspension was cooled with an ice-water bath. PhIO (80 mg,0.36 mmol) was added in several portions for 1 h, and the resulting light-brown suspension was stirred at 5°C for 1 h and then at rt for 5-15 h with monitoring the reaction by TLC. The reaction mixture was filtered, washed with CH2Cl2, and the combined filtrates were concentrated under reduced pressure to remove CH2Cl2. The residue was purified by silica gel chromatography, usually eluting with hexane-EtOAc mixture |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With tetrakis(μ-trifluoroacetamidato)dirhodium(II); iodosylbenzene In chlorobenzene at 5 - 20℃; Molecular sieve; Inert atmosphere; stereoselective reaction; | |
74% | Stage #1: (-)-menthol; 2,2,2-trichloroethyl sulfamate; D-glucal triacetate With tetrakis(μ-trifluoroacetamidato)dirhodium(II) In chlorobenzene Molecular sieve; Inert atmosphere; Stage #2: With iodosylbenzene In chlorobenzene at 5 - 20℃; Molecular sieve; Inert atmosphere; stereoselective reaction; | General procedure for one-pot amidoglycosylation General procedure: To a mixture of glycal 1a,b,c (0.2 mmol), alcohol (0.4 mmol),TcesNH2 (80 mg, 0.35 mmol), Rh2(NHCOCF3)4 (12 mg, 0.02 mmol),and activated powdered molecular sieves 4 Å (160 mg) under nitrogen was added PhCl (3 mL), and the resulting light-purple suspension was cooled with an ice-water bath. PhIO (80 mg,0.36 mmol) was added in several portions for 1 h, and the resulting light-brown suspension was stirred at 5°C for 1 h and then at rt for 5-15 h with monitoring the reaction by TLC. The reaction mixture was filtered, washed with CH2Cl2, and the combined filtrates were concentrated under reduced pressure to remove CH2Cl2. The residue was purified by silica gel chromatography, usually eluting with hexane-EtOAc mixture |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 58% 2: 22% | With tetrakis(μ-trifluoroacetamidato)dirhodium(II); magnesium oxide In chlorobenzene at 5℃; for 1h; | |
1: 58% 2: 22% | Stage #1: 1-Tetradecanol; 2,2,2-trichloroethyl sulfamate; D-glucal triacetate With tetrakis(μ-trifluoroacetamidato)dirhodium(II) In chlorobenzene Molecular sieve; Inert atmosphere; Stage #2: [bis(acetoxy)iodo]benzene In chlorobenzene at 5 - 20℃; Molecular sieve; Inert atmosphere; stereoselective reaction; | General procedure for one-pot amidoglycosylation General procedure: To a mixture of glycal 1a,b,c (0.2 mmol), alcohol (0.4 mmol),TcesNH2 (80 mg, 0.35 mmol), Rh2(NHCOCF3)4 (12 mg, 0.02 mmol),and activated powdered molecular sieves 4 Å (160 mg) under nitrogen was added PhCl (3 mL), and the resulting light-purple suspension was cooled with an ice-water bath. PhIO (80 mg,0.36 mmol) was added in several portions for 1 h, and the resulting light-brown suspension was stirred at 5°C for 1 h and then at rt for 5-15 h with monitoring the reaction by TLC. The reaction mixture was filtered, washed with CH2Cl2, and the combined filtrates were concentrated under reduced pressure to remove CH2Cl2. The residue was purified by silica gel chromatography, usually eluting with hexane-EtOAc mixture |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With tetrakis(μ-trifluoroacetamidato)dirhodium(II); iodosylbenzene In chlorobenzene at 5℃; for 1h; Molecular sieve; stereoselective reaction; | |
78% | Stage #1: 1-Tetradecanol; 2,2,2-trichloroethyl sulfamate; D-glucal triacetate With tetrakis(μ-trifluoroacetamidato)dirhodium(II) In chlorobenzene Molecular sieve; Inert atmosphere; Stage #2: With iodosylbenzene In chlorobenzene at 5 - 20℃; Molecular sieve; Inert atmosphere; stereoselective reaction; | General procedure for one-pot amidoglycosylation To a mixture of glycal 1a,b,c (0.2 mmol), alcohol (0.4 mmol),TcesNH2 (80 mg, 0.35 mmol), Rh2(NHCOCF3)4 (12 mg, 0.02 mmol),and activated powdered molecular sieves 4 Å (160 mg) under nitrogen was added PhCl (3 mL), and the resulting light-purple suspension was cooled with an ice-water bath. PhIO (80 mg,0.36 mmol) was added in several portions for 1 h, and the resulting light-brown suspension was stirred at 5°C for 1 h and then at rt for 5-15 h with monitoring the reaction by TLC. The reaction mixture was filtered, washed with CH2Cl2, and the combined filtrates were concentrated under reduced pressure to remove CH2Cl2. The residue was purified by silica gel chromatography, usually eluting with hexane-EtOAc mixture. 4.4.1. Tetradecyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxysulfonyl)amido-b-D-glucopyranoside (10a)Obtained in 78% yield as a colorless foam: Rf 0.35 (2:1 hexane/EtOAc); [a]D [25] 18.0 (c 2.2, CHCl3); 1H NMR (CDCl3): d 0.88 (t, 3H,J 6.9 Hz), 1.25 (s-like, 20H), 1.32 (m, 2H), 1.66 (quint, 2H,J 7.3 Hz), 2.04 (s, 3H), 2.10 (s, 3H), 2.13 (s, 3H), 3.56 (dt, 1H, J 9.3,7.1 Hz), 3.58 (q, 1H, J 9.0 Hz), 3.69 (ddd, 1H, J 2.3, 4.9, 8.8 Hz),3.88 (dt, 1H, J 9.4, 7.3 Hz), 4.14 (dd, 1H, J 2.3, 12.3 Hz), 4.27 (dd,1H, J 4.9, 12.3 Hz), 4.43 (d, 1H, J 8.2 Hz), 4.68 (d, 1H, J 10.9 Hz),4.72 (d, 1H, J 10.9 Hz), 5.08 (t, 1H, J 9.5 Hz), 5.12 (t, 1H,J 9.5 Hz), 5.36 (d, 1H, J 8.9 Hz) ppm; 13C NMR (CDCl3): d 14.1,20.6, 20.7, 20.8, 22.7, 25.8, 29.34, 29.36, 29.49, 29.58, 29.64, 31.9,59.0, 62.0, 68.4, 70.6, 71.8, 72.8, 78.7, 93.4, 100.8, 169.3, 170.7,171.6 ppm; MS (ESI): m/z calcd for C28H4835Cl3NO11S 711.20; found (%)734.21 ([M(35Cl3)Na], 97), 736.21 ([M(35Cl237Cl)Na], 100),738.16 ([M(35Cl37Cl2)Na], 43) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 65% 2: 25% | With zinc trifluoromethanesulfonate In 1,2-dichloro-ethane at 20℃; for 2h; Inert atmosphere; stereoselective reaction; | General procedure for the Zn(OTf)2-catalyzed Ferrier reaction General procedure: To a stirred solution of 3,4,6-tri-O-acetyl-D-glucal 1 (1 equiv) and acceptor (1.2 equiv) in anhydrous 1,2-dichloroethane(2 mL/mmol) under an atmosphere of argon was added Zn(OTf)2 (5-10 mol%) at room temperature. The reaction mixture was stirred until the complete consumption of the starting material (glycal). The solvent was filtered, filtrate was concentrated in vacuo, the crude residues were redissolved in dichloromethane and loaded on a silica gel column. The product was purifiedby silica gel chromatography using Hexane/EtOAc to afford the 2,3-unsaturated-glycosides asmajor product in excellent yields. All the Ferrier products were confirmed by IR, 1H NMR, 13CNMR and MS/HRMS spectroscopy. |
56 % de | With ruthenium trichloride In acetonitrile at 40℃; Inert atmosphere; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With zinc dibromide; In chloroform; at 72℃; for 0.25h;Microwave irradiation; | General procedure: In a typical reaction (Scheme 1), anhydrous ZnBr2(0.5 mmol) was added to a mixture of 3,4,6- tri-O-acetyl glucal (5 mmol) and a phenol or alcohol (4.5 mmol) in CHCl3(8 mL). A Teflon heating button and a stirring bar were introduced into the flask, which was then equipped with condenser and irradiated with microwave radiation(400 W) under open-vessel conditions in a Milestone START-S microwave labstation at 72C for a specified time period (Tables 1-5). After the completion of the reaction, water (15 ml) was added to the reaction mixture and the organic layer was separated. The aqueous layer was extracted with chloroform (25 ml). The combined organic layers was dried over anhydrous Na2SO4 and concentrated to afforda syrupy crude mass, which was refined by column chromatography on silica gel(100-200 mesh) using ethyl acetate (5-10%) in petroleum ether (60-80 C) as the eluent.The ratio of alpha and beta anomers, which had close Rf values and eluted together, was determined by integration of the corresponding hydrogen signals in the 1HNMR of the crude product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With zinc dibromide In chloroform at 72℃; for 0.666667h; Microwave irradiation; | General Procedure for Synthesis of Alkyl and Phenyl 2,3-Dideoxy-α-D-erythro-hex-2-enopyranoside Acetates General procedure: In a typical reaction (Scheme 1), anhydrous ZnBr2(0.5 mmol) was added to a mixture of 3,4,6- tri-O-acetyl glucal (5 mmol) and a phenol or alcohol (4.5 mmol) in CHCl3(8 mL). A Teflon heating button and a stirring bar were introduced into the flask, which was then equipped with condenser and irradiated with microwave radiation(400 W) under open-vessel conditions in a Milestone START-S microwave labstation at 72°C for a specified time period (Tables 1-5). After the completion of the reaction, water (15 ml) was added to the reaction mixture and the organic layer was separated. The aqueous layer was extracted with chloroform (25 ml). The combined organic layers was dried over anhydrous Na2SO4 and concentrated to afforda syrupy crude mass, which was refined by column chromatography on silica gel(100-200 mesh) using ethyl acetate (5-10%) in petroleum ether (60-80 C) as the eluent.The ratio of α and β anomers, which had close Rf values and eluted together, was determined by integration of the corresponding hydrogen signals in the 1HNMR of the crude product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With zinc dibromide; In chloroform; at 72℃; for 0.75h;Microwave irradiation; | General procedure: In a typical reaction (Scheme 1), anhydrous ZnBr2(0.5 mmol) was added to a mixture of 3,4,6- tri-O-acetyl glucal (5 mmol) and a phenol or alcohol (4.5 mmol) in CHCl3(8 mL). A Teflon heating button and a stirring bar were introduced into the flask, which was then equipped with condenser and irradiated with microwave radiation(400 W) under open-vessel conditions in a Milestone START-S microwave labstation at 72C for a specified time period (Tables 1-5). After the completion of the reaction, water (15 ml) was added to the reaction mixture and the organic layer was separated. The aqueous layer was extracted with chloroform (25 ml). The combined organic layers was dried over anhydrous Na2SO4 and concentrated to afforda syrupy crude mass, which was refined by column chromatography on silica gel(100-200 mesh) using ethyl acetate (5-10%) in petroleum ether (60-80 C) as the eluent.The ratio of alpha and beta anomers, which had close Rf values and eluted together, was determined by integration of the corresponding hydrogen signals in the 1HNMR of the crude product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With zinc dibromide; In chloroform; at 72℃; for 0.916667h;Microwave irradiation; | General procedure: In a typical reaction (Scheme 1), anhydrous ZnBr2(0.5 mmol) was added to a mixture of 3,4,6- tri-O-acetyl glucal (5 mmol) and a phenol or alcohol (4.5 mmol) in CHCl3(8 mL). A Teflon heating button and a stirring bar were introduced into the flask, which was then equipped with condenser and irradiated with microwave radiation(400 W) under open-vessel conditions in a Milestone START-S microwave labstation at 72C for a specified time period (Tables 1-5). After the completion of the reaction, water (15 ml) was added to the reaction mixture and the organic layer was separated. The aqueous layer was extracted with chloroform (25 ml). The combined organic layers was dried over anhydrous Na2SO4 and concentrated to afforda syrupy crude mass, which was refined by column chromatography on silica gel(100-200 mesh) using ethyl acetate (5-10%) in petroleum ether (60-80 C) as the eluent.The ratio of alpha and beta anomers, which had close Rf values and eluted together, was determined by integration of the corresponding hydrogen signals in the 1HNMR of the crude product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With iodine(I) bromide; In dichloromethane; toluene; at 0 - 20℃; for 1h;Inert atmosphere; | General procedure: A mixture of 3,4,6-tri-O-acetyl-D-glucal 1 (50.0 mg, 0.184 mmol) and alcohol (0.193 mmol) was dissolved in dry-CH2Cl2 : dry-toluene (125 : 200 muL) under gas-nitrogen. The solution was cooled to 0 C, then 0.5 M IBr in CH2Cl2 (20 mol%, 75 L) was added slowly. The stirring was continued at 0-20 C for 1-10 h. After TLC showed the completed conversion, the reaction mixture was quenched carefully with cooled aq.Na2S2O3 (20 mL) and washed with satd aq. NaHCO3 (20 mL), and extracted with EtOAc (3×20 mL). The combined organic layer was washed with brine (20 mL), dried over anhydrous Na2SO4, and then concentrated under reduced pressure. The residues were purified by silica gel column chromatography (EtOAc/n-hexane) to give the 2,3-unsaturated-O-glycoside products 2a-2t in good to high yields (71-99%). In most cases, a mixture of alpha and beta-anomers of glycoside 2 was obtained. The ratio of the isomers was determined by comparison of the integration values of the peaks in 1H NMR analysis. The alpha-configuration was characterized from the position of anomeric proton which appears in an up fieldposition compared to -anomer in most cases. The beta-isomers was not separated but characterized compared with the literature data of the mixture. Spectral data of pure alpha-isomers are as followed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74 % de | With zinc trifluoromethanesulfonate In 1,2-dichloro-ethane at 40℃; for 8h; Inert atmosphere; Green chemistry; Overall yield = 76 %; | General Procedure for Zn(OTf)2-mediated Azaglycosylation General procedure: To a stirred solution of glucal (1 equiv.) and N-nucleophile (1.1 equiv.) inanhydrous 1,2-dichloroethanne (2 mL/mmol) under an atmosphere of argon was added Zn(OTf)2 (10 mol%) at 40∘C. The reaction mixture was stirred untilthe complete consumption of the starting material (glycal). The solvent wasfiltered and concentrated in vacuo, and the crude residue was redissolved indichloromethane and loaded on a silica gel column. The product was purified by silica gel column chromatography using hexane/EtOAc as the eluent to affordthe 2,3-unsaturated N-glycosides. All of the products were confirmed by1H NMR, 13C NMR, and MS/HRMS spectroscopy and compared with that of literature data; characterization data of new products are outlined in the experimentalsection |
72 % de | With ruthenium trichloride In acetonitrile at 20℃; for 0.25h; Inert atmosphere; Overall yield = 74 %; | General procedure for the RuCl3-catalyzed N-glycosylation. General procedure: To a stirred solution of glycal (1.0 equiv) and N-nucleophile (1.2 equiv) in anhydrous acetonitrile (2 mL/mmol) under an atmosphere of argon was added RuCl3 (5 mol%) at room temperature. The reaction mixture was stirred until the complete consumption of the glycal as indicated by TLC. The reaction mixture was concentrated in vacuo, the crude residue was re-dissolved in dichloromethane and loaded on a silica gel column. The product was purified by silica gel chromatography using Hexane/EtOAc to afford the 2,3-unsaturated-N-glycosides as an inseparable α/β mixture or α-anomer in case of 3g,3g,3l. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With zinc trifluoromethanesulfonate; In 1,2-dichloro-ethane; at 40℃; for 5h;Inert atmosphere; Green chemistry; | General procedure: To a stirred solution of glucal (1 equiv.) and N-nucleophile (1.1 equiv.) inanhydrous 1,2-dichloroethanne (2 mL/mmol) under an atmosphere of argon was added Zn(OTf)2 (10 molpercent) at 40?C. The reaction mixture was stirred untilthe complete consumption of the starting material (glycal). The solvent wasfiltered and concentrated in vacuo, and the crude residue was redissolved indichloromethane and loaded on a silica gel column. The product was purified by silica gel column chromatography using hexane/EtOAc as the eluent to affordthe 2,3-unsaturated N-glycosides. All of the products were confirmed by1H NMR, 13C NMR, and MS/HRMS spectroscopy and compared with that of literature data; characterization data of new products are outlined in the experimentalsection | |
With ruthenium trichloride; In acetonitrile; at 20℃; for 3h;Inert atmosphere; | General procedure: To a stirred solution of glycal (1.0 equiv) and N-nucleophile (1.2 equiv) in anhydrous acetonitrile (2 mL/mmol) under an atmosphere of argon was added RuCl3 (5 molpercent) at room temperature. The reaction mixture was stirred until the complete consumption of the glycal as indicated by TLC. The reaction mixture was concentrated in vacuo, the crude residue was re-dissolved in dichloromethane and loaded on a silica gel column. The product was purified by silica gel chromatography using Hexane/EtOAc to afford the 2,3-unsaturated-N-glycosides as an inseparable alpha/beta mixture or alpha-anomer in case of 3g,3g,3l. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With zinc trifluoromethanesulfonate; In 1,2-dichloro-ethane; at 40℃; for 4h;Inert atmosphere; Green chemistry; | General procedure: To a stirred solution of glucal (1 equiv.) and N-nucleophile (1.1 equiv.) inanhydrous 1,2-dichloroethanne (2 mL/mmol) under an atmosphere of argon was added Zn(OTf)2 (10 mol%) at 40?C. The reaction mixture was stirred untilthe complete consumption of the starting material (glycal). The solvent wasfiltered and concentrated in vacuo, and the crude residue was redissolved indichloromethane and loaded on a silica gel column. The product was purified by silica gel column chromatography using hexane/EtOAc as the eluent to affordthe 2,3-unsaturated N-glycosides. All of the products were confirmed by1H NMR, 13C NMR, and MS/HRMS spectroscopy and compared with that of literature data; characterization data of new products are outlined in the experimentalsection | |
With ruthenium trichloride; In acetonitrile; at 20℃; for 0.75h;Inert atmosphere; | General procedure: To a stirred solution of glycal (1.0 equiv) and N-nucleophile (1.2 equiv) in anhydrous acetonitrile (2 mL/mmol) under an atmosphere of argon was added RuCl3 (5 mol%) at room temperature. The reaction mixture was stirred until the complete consumption of the glycal as indicated by TLC. The reaction mixture was concentrated in vacuo, the crude residue was re-dissolved in dichloromethane and loaded on a silica gel column. The product was purified by silica gel chromatography using Hexane/EtOAc to afford the 2,3-unsaturated-N-glycosides as an inseparable alpha/beta mixture or alpha-anomer in case of 3g,3g,3l. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With zinc trifluoromethanesulfonate; In 1,2-dichloro-ethane; at 40℃; for 6h;Inert atmosphere; Green chemistry; | General procedure: To a stirred solution of glucal (1 equiv.) and N-nucleophile (1.1 equiv.) inanhydrous 1,2-dichloroethanne (2 mL/mmol) under an atmosphere of argon was added Zn(OTf)2 (10 mol%) at 40?C. The reaction mixture was stirred untilthe complete consumption of the starting material (glycal). The solvent wasfiltered and concentrated in vacuo, and the crude residue was redissolved indichloromethane and loaded on a silica gel column. The product was purified by silica gel column chromatography using hexane/EtOAc as the eluent to affordthe 2,3-unsaturated N-glycosides. All of the products were confirmed by1H NMR, 13C NMR, and MS/HRMS spectroscopy and compared with that of literature data; characterization data of new products are outlined in the experimentalsection |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hafnium tetrakis(trifluoromethanesulfonate); In tetrahydrofuran; at 40℃; for 0.5h;Inert atmosphere; | General procedure: To a solution of D-glycal (200 mg, 1.0 eq) in anhydrous tetrahydrofuran (5 mL) under N2 atmosphere were added the acceptor (1.2 eq) and Hf(OTf)4 (10 mol%) at ambient temperature. The mixture was stirred at 40 C until complete consumption of the starting glycal. The reaction mixture was quenched with saturated sodium bicarbonate (5 mL) and extracted with CH2Cl2 (330 mL). The combined organics were washed with saturated salt water and dried over anhydrous Na2SO4. The solvent was removed under vacuum. The products were purified by silica gel column chromatograph with petroleum ether and ethyl acetate as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With hafnium tetrakis(trifluoromethanesulfonate); In tetrahydrofuran; at 40℃; for 0.416667h;Inert atmosphere; | General procedure: To a solution of D-glycal (200 mg, 1.0 eq) in anhydrous tetrahydrofuran (5 mL) under N2 atmosphere were added the acceptor (1.2 eq) and Hf(OTf)4 (10 mol%) at ambient temperature. The mixture was stirred at 40 C until complete consumption of the starting glycal. The reaction mixture was quenched with saturated sodium bicarbonate (5 mL) and extracted with CH2Cl2 (330 mL). The combined organics were washed with saturated salt water and dried over anhydrous Na2SO4. The solvent was removed under vacuum. The products were purified by silica gel column chromatograph with petroleum ether and ethyl acetate as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With hafnium tetrakis(trifluoromethanesulfonate) In tetrahydrofuran at 40℃; for 0.5h; Inert atmosphere; stereoselective reaction; | General experimental procedure of Ferrier rearrangement General procedure: To a solution of D-glycal (200 mg, 1.0 eq) in anhydrous tetrahydrofuran (5 mL) under N2 atmosphere were added the acceptor (1.2 eq) and Hf(OTf)4 (10 mol%) at ambient temperature. The mixture was stirred at 40 °C until complete consumption of the starting glycal. The reaction mixture was quenched with saturated sodium bicarbonate (5 mL) and extracted with CH2Cl2 (330 mL). The combined organics were washed with saturated salt water and dried over anhydrous Na2SO4. The solvent was removed under vacuum. The products were purified by silica gel column chromatograph with petroleum ether and ethyl acetate as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trimethylsilyl bromide; Triphenylphosphine oxide; In dichloromethane; at 20℃; under 760.051 Torr;Inert atmosphere; | General procedure: Glycals (50.0mg, 1.0 equiv), acceptors (12-24, 2.0 equiv), and triphenylphosphine oxide (TPPO, 1.0 equiv) were mixed in a flame dried flask. After the reagents became homogeneous, TMSBr (1.0 equiv) was slowly added at room temperature under ambient atmosphere. After stirring for 1 to 2 hours, the mixture was directly purified by flash column chromatography on silica gel and then volatiles were removed in vacuo to affordexpected products. The products and yields are shown in Tables 2-4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.889 % de | Stage #1: 2,2,2-trichloroethyl sulfamate; D-glucal triacetate With tetrakis(μ-trifluoroacetamidato)dirhodium(II); magnesium oxide In chlorobenzene Inert atmosphere; Stage #2: [bis(acetoxy)iodo]benzene In chlorobenzene at 5 - 20℃; for 12h; Inert atmosphere; Overall yield = 91 %; stereoselective reaction; | General procedure for amidoacetoxylation To a mixture of glycal 1a,b,c (0.2 mmol), R-NH2 (R= Tces, Ns, Ts,or Troc) (0.35 mmol), Rh2(NHCOCF3)4 (12 mg, 0.02 mmol), and MgO(32 mg, 0.8 mmol) under nitrogen was added PhCl (3 mL), and the resulting light-purple suspension was cooled with an ice-waterbath. PhI(OAc)2 (80 mg, 0.36 mmol) was added in several portionsfor 1 h, and the resulting light-brown suspension was stirredat 5°C for 1 h and then at rt for 10 h. The reaction mixture was filtered, washed with CH2Cl2, and the combined filtrates were concentrated under reduced pressure. The residue was purified by silica gel chromatography eluting with hexane-EtOAc mixture. 4.2.1. 1,3,4,6-Tetra-O-Acetyl-2-deoxy-2-(2,2,2-trichloroethoxysulfonyl)amido-β-D-glucopyranose (2a-b) Obtained in 91% yield (β/α= 17) as a colorless foam: Rf 0.28 (3:2hexane/EtOAc); [a]D [25] 9.0 (c 1.0, CHCl3); 1HNMR (CDCl3): d 2.06(s, 3H), 2.10 (s, 3H), 2.15 (s, 3H), 2.22 (s, 3H), 3.78 (dt, 1H, J 10.4,9.0 Hz), 3.87 (ddd, 1H, J 2.2, 4.5, 9.9 Hz), 4.12 (dd, 1H, J 2.2,12.5 Hz), 4.28 (dd, 1H, J 4.5, 12.5 Hz), 4.61 (d, 1H, J 11.0 Hz), 4.64 (d,1H, J 11.0 Hz), 5.11 (t,1H, J 9.7 Hz), 5.20 (t,1H, J 9.9 Hz), 5.71(d, 1H, J 8.7 Hz), 5.81 (d, 1H, J 9.0 Hz) ppm; 13C NMR (CDCl3):d 20.5, 20.7, 20.8, 21.0, 57.9, 61.5, 67.9, 72.4, 72.6, 78.6, 92.0, 93.2,169.4, 169.7, 170.7, 171.8 ppm |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | Stage #1: 2,3-dihydro-2,2-dimethylbenzo[b]pyran-4-one With t-butyldimethylsiyl triflate; N-ethyl-N,N-diisopropylamine In dichloromethane for 0.333333h; Inert atmosphere; Stage #2: D-glucal triacetate In dichloromethane at 0 - 30℃; Inert atmosphere; Overall yield = 66 %; Overall yield = 291 mg; diastereoselective reaction; | (I) General information for the synthesis of glucopyranoside. General procedure: To an oven-dried 10-mL round-bottomed flask under N2 wasadded CH2Cl2 (5.0 mL), Acetophenone/chromanone (1.0 mmol,200 mg), iPr2NEt (234 mL, 1.20 mmol), TBSOTf (324 mL 1.25 mmol).After 20 min, protected sugar (1.1 mmol 335 mg) was added at 0 C,and the mixture was stirred at room temperature for the indicatedtime. The reaction mixture was passed through a silica gel plug(1 cm 5 cm) with Et2O and was neutralized by aqueous NaHCO3solution. The Et2O extract was removed by rotary evaporation. Theproduct was purified by silica gel chromatography (10e15% EtOAc/hexanes) from which only the major product was isolated. Thespectral data of representative compounds are shown below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With hafnium tetrakis(trifluoromethanesulfonate); In acetonitrile; at -20℃; for 0.333333h; | General procedure: To a stirred solution of 3,4,6-tri-O-acetyl-D-glucal (188 mg, 0.7 mmol), 3,4,6-tri-O-benzyl-D-glucal (292 mg, 0.7 mmol) or ((2R,3S)-3-acetoxy-2,3-dihydrofuran-2-yl)methyl acetate (140 mg, 0.7 mmol) and the corresponding nucleophile (1.3 eq) in CH3CN (5 mL) were added Hf(OTf)4 (10 mol%) at -20oC. The mixture was stirred under -20oC for the appropriate amount of time (Table 2 and 3), and the extent of the reaction was monitored by TLC analysis. The reaction mixture was diluted with cooled sodium bicarbonate (sat., 20 mL) and extracted with DCM (3 x 10 mL). The combined organics were dried over anhydrous Na2SO4. The solvent was removed under vacuum. All the products were purified by silica gel column chromatography (hexane / EtOAc=6 / 1). 4,6-Di-O-acetyl-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranosyl-<strong>[4563-33-1]benzylsulfonamide</strong> (3a). Colorless oil; [alpha]D25 = +104.5 (c 1.81, CHCl3, alpha only) { lit.4a: [alpha]D10=+44.9 (c 0.96,CHCl3,alpha:beta=10:1) }; 1H NMR (400 MHz, CDCl3) delta 7.38-7.35 (m, 2H), 7.25 (s, 3H), 5.81 (d, J = 6.4 Hz, 1H), 5.69 (d, J = 9.9 Hz, 1H), 5.40 (s, 1H), 5.18 (d, J = 55.6 Hz, 2H), 4.49 - 4.29 (m, 1H), 4.17 (d, J = 11.2 Hz, 2H), 4.09 - 3.77 (m, 2H), 1.97 (d, J = 2.3 Hz, 6H) ppm; IR(film,cm-1): 3273, 2930, 1741, 1556, 1440, 1331, 1235, 1152, 1040, 973, 905, 784, 736; MS(ESI) m/z: 401.1 ([M+NH4]+,100). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With Fe3O4(at)C-SO3H; In 1,2-dichloro-ethane; at 80℃; for 1h;Green chemistry; | General procedure: Typically, to a mixture of tri-O-acetyl-D-glucal (0.2 mmol, 54.4 mg)and benzyl alcohol (26 muL, 0.24 mmol) and Fe3O4C-SO3H (30 mol%,25mg) in a round bottom flask (10 mL), dichloroethane (2 mL) wasadded and the reaction mixture was stirred for 10min at 80 C. Aftercompletion of the reaction(monitored by TLC), the catalyst is separatedfrom the reaction with an external magnetic force and the catalyst was washed with dichloromethane. The organic phase was combined andcondensed under vacuum to get crude product, which was purified bysilica gel column chromatography (petroleum ether/EtOAc = 6/1) to get3a in 96% yield. All new compounds were fully characterized by NMRand MS. Spectral and analytical data were in good agreement with thedesired structures. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With erbium(III) triflate In 2-methyltetrahydrofuran at 60℃; for 4h; Green chemistry; diastereoselective reaction; | General Procedure one pot tosylation/azaglycosidation reaction of amine with 3,4,5-tri-O-acetyl-D-glucal. General procedure: To a stirred solution of tosyl chloride (2.2 mmol), in 2-MeTHF (3 mL) was added the N-nucleophile (2.0 mmol) and Er(OTf)3 (0.2 mmol). The reaction was conducted in a two neck round bottom flask using a reflux system. The reaction process was monitored by TLC using ultraviolet illumination at 254 nm allowed for visualization for UV active materials or staining with ninhydrin solution allowed for further visualization. After 2 hours is added 2 mmol of tri-O-acetyl-D-glucal and it is left in the same conditions for another 2 hours. The reaction mixture was extracted with H2O and the organic phase (2-MeTHF as solvent), then dried over Na2SO4. The crude material was dried under vacuum (~1 mmHg) and purified by flash chromatography on silicagel (CHCl3/EtOH 9.5/0.5) to isolate the desired product. Methyl-2-(4,6-Di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl-N-p-toluenesulfonamide)-propanoate (1a). yellow oil obtained in 80 % yield; 1H NMR (300 MHz, CDCl3): d= 7.76 (d, 2H, J = 8.2, Ar), 7.32 (d, 2H, J = 8.2, Ar), 5.94 (dd, 1H, J=9.3, 6.1 Hz, H-3), 5.82 (ddd, J=9.3, J=8.1, 1.7 Hz, 1H, H-2), 5.47-5.45 (m, 1H, H-4), 5.28 (d, J=8.1, Hz, 1H, H-1), 4.24-4.22 (m, 2H, H-6), 4.19-4.17 (m, 1H, H-5), 3.99-4.01 (m, J=7.1 Hz, 1H, CH-N), 3.55 (s, 3H, CH3COO), 2.43 (s, 3H, CH3Ph), 2.10 (s, 3H, CH3COO), 2.07 (s, 3H, CH3COO). 13C NMR (75 MHz, CDCl3): d= 172.7 (C=O), 170.4 (C=O), 170.0 (C=O), 143.6 (C), 138.1 (H), 130.2 (CH), 133.9 (CH), 127.5 (CH), 127.5 (2 CH), 68.0 (CH-1), 63.9 (CH-5), 63.4 (CH-4), 63.2 (CH2-6), 52.4 (CH3), 51.8 (CH), 21.4 (CH3), 20.8 (CH3COO), 20.6 (CH3COO), 19.9 (CH3). IR (neat) : 3440, 3019, 2400, 1741, 1216, 1045, 749, 669. Anal. Calcd for C21H27NO9S: C 53.72, H 4.80, N 2.98. Found C 53.80, H 4.76, N 2.95. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50 % de | Stage #1: 4-(4-benzyloxyphenyl) iodide With n-butyllithium In n-heptane; toluene at 0℃; for 0.416667h; Schlenk technique; Inert atmosphere; Stage #2: With Br3LiZn In n-heptane; dibutyl ether; toluene at 0℃; for 0.416667h; Schlenk technique; Inert atmosphere; Stage #3: D-glucal triacetate In n-heptane; dibutyl ether; toluene at 80℃; for 1h; Schlenk technique; Inert atmosphere; Overall yield = 52 %; diastereoselective reaction; | General Procedure for the Synthesis of Dihydropyrans 6a-c,7a-g, and 8a,b General procedure: A 25 mL Schlenk tube was equipped with magnetic agitationunder inert atmosphere (N2). The corresponding iodo compound(1.1 equiv) was dissolved in toluene (4 L/mol). Aftercooling the mixture to 0 °C with an ice-bath, n-BuLi (1.15 equiv,25% w/w in heptane) was added over 5 min. After 20 min,ZnBr2·LiBr (1.15 equiv, 32% w/w in DBE) was added over 5 minat 0 °C. After 20 min, a toluene solution of glycal substrate (1.0equiv, 1 L/mol) was added at 0 °C. The reaction was stirred at r.t.and followed by TLC until starting material was completely consumed(1-5 h). After completion, the reaction medium wasquenched with saturated NH4Cl (aq) (4 L/mol) for 30 min, andphases were separated. The aqueous phase was extracted threetimes with EtOAc. All organic layers were combined and driedover Na2SO4, filtered, and finally put under reduced pressure toremove volatile materials. The diastereomeric ratio was determinedfrom the crude mixture based on the 1H NMR spectrumanalysis. After evaporation, purification on silica gel by flashcolumn chromatography afforded the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With [bis(acetoxy)iodo]benzene; palladium diacetate; In acetonitrile; at 120℃; for 12h;Sealed tube; | General procedure: To a stirred solution of tri-O-acetyl-D-glucal (0.5 mmol), palladium acetate (0.025 mmol), PhI(OAc)2 (0.5 mmol) was added aromatic acid (1 mmol). The resulting mixture was heated in a sealed tube at 120 C in dry acetonitrile (10 mL) for 12h. After completion, the solvent was removed under reduced pressure and diluted with ethyl acetate (2 mL), washed with aqueous NaHCO3 (5 mL) followed by water and brine solution (5 mL). The organic layer was evaporated and the residue was purified by flash column chromatography (hexane/EtOAc = 7/3) to afford the product as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With [bis(acetoxy)iodo]benzene; palladium diacetate; In acetonitrile; at 120℃; for 12h;Sealed tube; | General procedure: To a stirred solution of tri-O-acetyl-D-glucal (0.5 mmol), palladium acetate (0.025 mmol), PhI(OAc)2 (0.5 mmol) was added aromatic acid (1 mmol). The resulting mixture was heated in a sealed tube at 120 C in dry acetonitrile (10 mL) for 12h. After completion, the solvent was removed under reduced pressure and diluted with ethyl acetate (2 mL), washed with aqueous NaHCO3 (5 mL) followed by water and brine solution (5 mL). The organic layer was evaporated and the residue was purified by flash column chromatography (hexane/EtOAc = 7/3) to afford the product as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With [bis(acetoxy)iodo]benzene; palladium diacetate; In acetonitrile; at 120℃; for 12h;Sealed tube; | General procedure: To a stirred solution of tri-O-acetyl-D-glucal (0.5 mmol), palladium acetate (0.025 mmol), PhI(OAc)2 (0.5 mmol) was added aromatic acid (1 mmol). The resulting mixture was heated in a sealed tube at 120 C in dry acetonitrile (10 mL) for 12h. After completion, the solvent was removed under reduced pressure and diluted with ethyl acetate (2 mL), washed with aqueous NaHCO3 (5 mL) followed by water and brine solution (5 mL). The organic layer was evaporated and the residue was purified by flash column chromatography (hexane/EtOAc = 7/3) to afford the product as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29% | With bis-triphenylphosphine-palladium(II) chloride; tetrabutyl-ammonium chloride; triethylamine In N,N-dimethyl-formamide at 125℃; for 48h; Sealed tube; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81.818 % de | With Fe(III) immobilized on Fe3O4 nanoparticles-coated carbon shell In 1,2-dichloro-ethane at 25℃; for 0.166667h; Green chemistry; Overall yield = 86percent; | General procedure for unsaturated sugars 3a-3r General procedure: To a mixture of 3,4,6-tri-O-acetyl-D-glucal (1 mmol) and acceptor 2a-2r (1.2 mmol) in solvent (10mL) was addedFe3O4CFe((at)) catalyst and stirred at room temperature. On consumption of glucal (TLC monitoring), thereaction mixture and catalyst was separated and evaporated to give a crude product which was purified by silicagel column chromatography. |
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H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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