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[ CAS No. 114861-14-2 ] {[proInfo.proName]}

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Chemical Structure| 114861-14-2
Chemical Structure| 114861-14-2
Structure of 114861-14-2 * Storage: {[proInfo.prStorage]}
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Product Details of [ 114861-14-2 ]

CAS No. :114861-14-2 MDL No. :MFCD22666287
Formula : C24H32O5Si Boiling Point : -
Linear Structure Formula :- InChI Key :XJKAZNSYWAGYDQ-CIAFKFPVSA-N
M.W : 428.59 Pubchem ID :11102029
Synonyms :

Calculated chemistry of [ 114861-14-2 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 30
Num. arom. heavy atoms : 12
Fraction Csp3 : 0.5
Num. rotatable bonds : 6
Num. H-bond acceptors : 5.0
Num. H-bond donors : 1.0
Molar Refractivity : 119.02
TPSA : 57.15 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : Yes
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.4 cm/s

Lipophilicity

Log Po/w (iLOGP) : 3.91
Log Po/w (XLOGP3) : 4.95
Log Po/w (WLOGP) : 2.8
Log Po/w (MLOGP) : 2.59
Log Po/w (SILICOS-IT) : 2.56
Consensus Log Po/w : 3.36

Druglikeness

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

Water Solubility

Log S (ESOL) : -5.52
Solubility : 0.00131 mg/ml ; 0.00000305 mol/l
Class : Moderately soluble
Log S (Ali) : -5.89
Solubility : 0.000555 mg/ml ; 0.00000129 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -6.14
Solubility : 0.000312 mg/ml ; 0.000000728 mol/l
Class : Poorly soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 6.21

Safety of [ 114861-14-2 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P280-P301+P312-P302+P352-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 114861-14-2 ]

* 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 [ 114861-14-2 ]

[ 114861-14-2 ] Synthesis Path-Downstream   1~51

  • 1
  • [ 114861-14-2 ]
  • [ 114861-17-5 ]
YieldReaction ConditionsOperation in experiment
With pyridine; trifluoromethylsulfonic anhydride; tetra-(n-butyl)ammonium iodide 1.) CH2Cl2, -10 deg C, 15 min; 2.) benzene, reflux, 12 h; Yield given. Multistep reaction;
  • 2
  • [ 114861-14-2 ]
  • [ 190970-10-6 ]
YieldReaction ConditionsOperation in experiment
With sodium tetrahydroborate; acetic anhydride; dimethyl sulfoxide Yield given. Multistep reaction;
With sodium tetrahydroborate In ethanol Yield given;
Multi-step reaction with 2 steps 1: acetic anhydride / dimethylsulfoxide / 20 °C 2: 6.31 g / NaBH4 / CH2Cl2; methanol / 0.5 h / 0 °C
Multi-step reaction with 2 steps 1: DMSO, Ac2O / 16 h 2: NaBH4 / methanol; CH2Cl2
Multi-step reaction with 2 steps 1.1: oxalyl dichloride / dichloromethane; dimethyl sulfoxide / 0.58 h / -60 °C / Inert atmosphere 1.2: 3.5 h / -60 - 20 °C / Inert atmosphere 2.1: sodium tetrahydroborate / water; ethanol / 4 h / 0 °C / Inert atmosphere
Stage #1: 1,2-O-isopropylidene-5-O-(t-butyldiphenylsilyl)-α-D-xylofuranose With acetic anhydride In dimethyl sulfoxide for 16h; Stage #2: With sodium tetrahydroborate In methanol; dichloromethane at 0℃; for 0.0833333h; 2 alcohol 22 A solution of 21 (27.2 g, 63.7 mmol’) in DMS() (200 mL) and Ac20 (50 niL) is stirred for 16 hour before pouring into ice water (200 mL). The mixture is extracted with diethi ether (100 mL x 3) and the combined organic layers are washed with sodium bicarbonate aqueous solution (10%, 100 mL) and water (100 mL), and concentrated. The residue is then dissolved in MeOH (250 mL) and DCM (250 mL) at 0 °C followed by addition of sodium borohydride (12.0 g) in 10 portions. After stirring for 5 minutes, water (100 mL) is added and the layers are separated. The organic layer is then concentrated and purified by silica gel column chromatography” (diethvi ether/PE ‘ 1/2) to give 22 as a white solid (20.4 g, 75% yield over two steps). (MS: [M+Na 451.2)
Multi-step reaction with 2 steps 1.1: oxalyl dichloride; N,N-dimethyl-formamide / dichloromethane / 0.5 h / -60 °C 1.2: 3 h / -60 - 20 °C 2.1: sodium tetrahydroborate / water / 12 h / 0 - 20 °C

  • 4
  • [ 20031-21-4 ]
  • [ 58479-61-1 ]
  • [ 114861-14-2 ]
YieldReaction ConditionsOperation in experiment
100% With 1H-imidazole In N,N-dimethyl-formamide at 0 - 20℃; for 1.16667h; Inert atmosphere;
100% With 1H-imidazole In N,N-dimethyl-formamide at 20℃; for 1h; 25 1,2-O-isopropylidene-5-O-t-butyldiphenylsilyl-α-D-xylofuranose (31) A mixture of 1,2-O-isopropylidene-α-D-xylofuranose (38.0 g, 0.2 mol), t-butyl-diphenylchlorosilane (70 g, 0.25 mol) and imidazole (21.5 g, 0.4 mol) in N,N-dimethyl-formamide (50 mL) is stirred at room temperature for 1 hour. The solvent is removed in vacuo, and the residue is dissolved in ethyl acetate (1 L), and extracted with water (300 mL*2) and brine (300 mL), dried over sodium sulfate, and concentrated to dryness in vacuo to give crude 31 (86 g, 100%), which is used directly in the next step without further purification.
99% Stage #1: 1,2-O-isopropylidene-α-D-xylose With 1H-imidazole In N,N-dimethyl-formamide for 0.25h; Inert atmosphere; Cooling with ice; Stage #2: tert-butylchlorodiphenylsilane In N,N-dimethyl-formamide for 1h; Inert atmosphere; Synthesis of 1,2-O-isopropylidene-5-O-TBDPS-α-D-xylofuranose (I)2 1,2-O-isopropylidene-α-D-xylofuranose (11.41 g, 60 mmol) was dissolved in anhydrous DMF (300 mL) under Argon. Next imidazole (10.21 g, 150 mmol) was added and the mixture was cooled in an ice bath. After 15 min, TBDPSiCl (20.30 mL, 78 mmol) was added and the ice bath removed. TLC analysis (25 % EA / Hex; Rf = 0.33) showed full conversion after 1 hour. Water was added and the mixture evaporated till dryness. The residue was taken up in EA (300 mL) and water (150 mL). The layers were separated and the organic layer was sequentially washed with sat. NH4Cl sol. (150 mL), sat. NaHCO3 sol. (150 mL) and brine (150 mL). The organic layer was dried over Na2SO4, filtered and evaporated till dry. The mixture was purified by column chromatography (10 % → 30 % EA / Hex). The product (25.5 g, 59.5 mmol) was isolated as white waxy solid (99% yield).
98% With pyridine for 18h; Ambient temperature;
98% With TEA In N,N-dimethyl-formamide at 20℃;
96% With 1H-imidazole In N,N-dimethyl-formamide at 0 - 25℃; for 2h;
95% With pyridine for 3h;
95%
95% With pyridine; 1H-imidazole for 3h; 1 alcohol 21 To a solution of 20 (12.8 g, 67.0 mrnol) in Py (300 mL) is added TBDPSC1 (21.0 mL, 80.4 rnmoi). After stirring for 3 h, MeOH (25 mL) is added and the mixture is concentrated. The residue is dissolved in diethyl ether (200 mL), washes with sodium bicarbonate aqueous solution (10%, 100 mL) and water (100 mL), dried, over anhvdrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography (diethy”l ether/PE = 1/2)to give 21 as awhite solid (27.2 g, 95%yield). (MS: M+Na 451.2)
94% With 1H-imidazole In N,N-dimethyl-formamide for 1h; Ambient temperature;
94.7% With 1H-imidazole In N,N-dimethyl-formamide at 25℃; for 1h;
88% With dmap; TEA In dichloromethane
88.7% With 1H-imidazole In N,N-dimethyl-formamide at 0 - 25℃; for 5h; Inert atmosphere; 100.1 Step 1: To a solution of 1,2-0-(1-Methylethylidene-a-D-xylofuranose (40 g, 210.31 mmol, 1eq.) in DMF (300 mL) was added imidazole (35.80 g, 525.78 mmol, 2.5 eq.) and TBDPSCl(69.37 g, 252.37 mmol, 64.83 mL, 1.2 eq.) at 0°C underN2 atomsphere. The mixture wasstirred at 25°C for 5 h before it was quenched with H20 (1000 mL). The aqueous phase wasextracted with EtOAc (3 x 250 mL). The combined organic layer was washed with brine(500 mL), dried over Na2S04 and filtered. The filtrate was concentrated to dryness. Thecrude product was purified by flash silica gel chromatography to provide the product( 3aR, 5R, 6S, 6aR)-5-( ( (tert-butyldi phenylsilyl )oxy )methyl )-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-ol (80 g, 88.7% yield) as a colorless syrup.
83% With pyridine; dmap at 20℃; for 16h;
75% With 1H-imidazole In dichloromethane at 0 - 20℃; Inert atmosphere;
75% With 1H-imidazole In N,N-dimethyl-formamide
60% With 1H-imidazole In pentane for 3h; Ambient temperature;
With 1H-imidazole In N,N-dimethyl-formamide at 20℃; for 12h;
With pyridine at 20℃; Inert atmosphere; 2 Step 2: Into a 10L 4-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen was added a solution of (3aR,5R,6S,6aR)-5-(hydroxymethyl)-2,2-dimethyl- tetrahydro-2H-furo[2,3-d][1,3]dioxol-6-ol (951 g, 5 mol) in pyridine (7 L) and tert- butyl(chloro)diphenylsilane (1404 g, 5.1 mol). The resulting solution was stirred overnight at room temperature. To the solution was added 600 mL of MeOH. The resulting mixture was concentrated under reduced pressure. The residue was solubilized in EtOAc, washed with HCl (0.5 M), saturated NaHCO3and brine. The organic layer was dried over Na2SO4, andconcentrated under reduced pressure to give (3aR,5R,6S,6aR)-5-[[(tert- butyldiphenylsilyl)oxy]methyl]-2,2-dimethyl-tetrahydro-2H-furo[2,3-d][1,3]dioxol-6-ol as an oil. MS: 451 [M+Na]+.
With 1H-imidazole In N,N-dimethyl-formamide at 0 - 20℃; for 4h; 1 first step Add 1,2-O-isopropylidene-α-D-xylofuranose (5.70 g, 29.99 mmol) into a 150mL two-neck bottle,Imidazole (5.76 g, 84.65 mmol) and 30 mL of ultra-dry N,N-dimethylformamide. Place the reaction flask in an ice bath at 0°C, and then add tert-butyldiphenylchlorosilane (10mL, 38.46 mmol) dropwise. The addition is complete. The reaction is stirred at room temperature for 4 h, and water (100 mL ) And ethyl acetate (50 mL), extracted with ethyl acetate (50 mL×2), the combined organic phase was washed with saturated brine (50 mL×2), dried by adding anhydrous Na2SO4, filtered, and separated by column chromatography ( PE:EA = 30:1 to 6:1), a colorless liquid is obtained, which is indeed the target product after NMR identification.

Reference: [1]Beahm, Brendan J.; Dehnert, Karen W.; Derr, Nicolas L.; Kuhn, Joachim; Eberhart, Johann K.; Spillmann, Dorothe; Amacher, Sharon L.; Bertozzi, Carolyn R. [Angewandte Chemie - International Edition, 2014, vol. 53, # 13, p. 3347 - 3352][Angew. Chem., 2014, vol. 53, # 13, p. 3347 - 3352,6]
[2]Current Patent Assignee: GILEAD SCIENCES INC - US10100076, 2018, B2 Location in patent: Page/Page column 148
[3]Hulpia, Fabian; Balzarini, Jan; Schols, Dominique; Andrei, Graciela; Snoeck, Robert; Van Calenbergh, Serge [Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 8, p. 1970 - 1972]
[4]McDevitt, Jason P.; Lansbury Jr., Peter T. [Journal of the American Chemical Society, 1996, vol. 118, # 16, p. 3818 - 3828]
[5]Hall, Adrian; Bailey, Patrick D.; Rees, David C.; Rosair, Georgina M.; Wightman, Richard H. [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 3, p. 329 - 343]
[6]Nicolaou, K. C.; Daines, R. A.; Uenishi, J.; Li, W. S.; Papahatjis, D. P.; Chakraborty, T. K. [Journal of the American Chemical Society, 1987, vol. 109, # 7, p. 2205 - 2208]
[7]Van Straten, Nicole C. R.; Van der Marel, Gijsbert A.; Van Boom, Jacques H. [Tetrahedron, 1997, vol. 53, # 18, p. 6509 - 6522]
[8]Moon Woo Chun; Myung Jung Kim; Un Hee Jo; Joong Hyup Kim; Kim; Lak Shin Jeong [Nucleosides, nucleotides and nucleic acids, 2001, vol. 20, # 4-7, p. 703 - 706]
[9]Current Patent Assignee: IMMUNE SENSOR LLC; THE UNIVERSITY OF TEXAS SYSTEM - WO2017/161349, 2017, A1 Location in patent: Paragraph 0232
[10]Nicolaou, K. C.; Daines, R. A.; Uenishi, J.; Li, W. S.; Papahatjis, D. P.; Chakraborty, T. K. [Journal of the American Chemical Society, 1988, vol. 110, # 14, p. 4672 - 4685]
[11]Kim, Jaeseung; Weledji, Yvonne N.; Greenberg, Marc M. [Journal of Organic Chemistry, 2004, vol. 69, # 18, p. 6100 - 6104]
[12]Hoeffler, Jean-François; Grosdemange-Billiard, Catherine; Rohmer, Michel [Tetrahedron Letters, 2000, vol. 41, # 25, p. 4885 - 4889]
[13]Current Patent Assignee: CALITHERA BIOSCIENCES INC - WO2018/119284, 2018, A1 Location in patent: Page/Page column 222
[14]Baszczyňski, Ondřej; Watt, Joanna M.; Rozewitz, Monika D.; Guse, Andreas H.; Fliegert, Ralf; Potter, Barry V.L. [Journal of Organic Chemistry, 2019, vol. 84, # 10, p. 6143 - 6157]
[15]Gopishetty, Bhaskar; Zhu, Jinge; Rajan, Rakhi; Sobczak, Adam J.; Wnuk, Stanislaw F.; et al. [Journal of the American Chemical Society, 2009, vol. 131, p. 1243 - 1250]
[16]Ler, Geraldine J. M.; Xu, Weijun; Mak, Jeffrey Y. W.; Liu, Ligong; Bernhardt, Paul V.; Fairlie, David P. [Chemistry - A European Journal, 2019, vol. 25, # 68, p. 15594 - 15608]
[17]Botta, Oliver; Moyroud, Elisabeth; Lobato, Cinta; Strazewski, Peter [Tetrahedron, 1998, vol. 54, # 44, p. 13529 - 13546]
[18]Van Straten, Nicole C.R.; Van Der Marel, Gijsbert A.; Van Boom, Jacques H. [Tetrahedron Letters, 1996, vol. 37, # 20, p. 3599 - 3602]
[19]Choi, Sei-Hyun; Mansoorabadi, Steven O.; Liu, Yung-Nan; Chien, Tun-Cheng; Liu, Hung-Wen [Journal of the American Chemical Society, 2012, vol. 134, # 34, p. 13946 - 13949]
[20]Current Patent Assignee: WAN MRRAY; MERCK & CO INC - WO2020/33285, 2020, A1 Location in patent: Page/Page column 59; 60
[21]Current Patent Assignee: ALI CHEMICAL CHANGZHOU CO LTD - CN112661802, 2021, A Location in patent: Paragraph 0016-0017
  • 6
  • [ 114861-14-2 ]
  • [ 75783-45-8 ]
YieldReaction ConditionsOperation in experiment
100% With chromium(VI) oxide; acetic anhydride In pyridine; dichloromethane at 20℃; 1 Preparation of Compound 2a: [00325] To a stirred solution of chromium (VI) oxide (500 mmol) in anhydrous dichloromethane (1400 mL) were added dropwise at 0°C acetic anhydride (524 mmol) and anhydrous pyridine (86 mL). The reaction mixture was stirred at room temperature during 30 minutes. Compound la (163 mmol) in dichloromethane (200 mL) was added dropwise and the reaction mixture was stirred at room temperature overnight. The mixture was poured on cold ethyl acetate (2000 mL) and precipitated salts were filtered on a silica gel cake. The filtrate was concentrated under reduced pressure and co-evaporated with toluene and dried under high vacuum overnight to give the expected compound as an oil in quantitative yield (TLC control).
99% With 4 A molecular sieve; pyridinium chlorochromate In dichloromethane at 20℃; for 60h;
93% With Dess-Martin periodane In dichloromethane at 0 - 25℃; for 16h; 100.2 Step 2: To a solution of (3aR,5R,6S, 6aR)-5-(((tert-butyldiphenylsilyl)oxy)methyl)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-ol (80 g, 186.66 mmol, 1 eq.) in DCM (1000 mL)was added DMP (118.75 g, 279.99 mmol, 86.68 mL, 1.5 eq.) at 0°C. The mixture was stirredat 25°C for 16 h to give a white suspension. The mixture was quenched with saturated aq.Na2S203 (500 mL). The aqueous phase was extracted with DCM (2 x 500 mL). Thecombined organic layer was washed with brine (500 mL), dried over Na2S04, filtered and concentrated to dryness. The crude product was purified by silica gel columnchromatography (0- 17% ofEtOAc in petroleum ether) to provide (3aR,5R, 6aS)-5-(((tertbutyldiphenylsilyl)oxy)methyl)-2,2-dimethyldihydrofuro[2,3-d][1,3]dioxol-6(3aH)-one (74.1g, 93% yield) was obtained as a colorless gum.
With acetic anhydride; dimethyl sulfoxide
With acetic anhydride; dimethyl sulfoxide for 16h;
With oxalyl dichloride; TEA; dimethyl sulfoxide In tetrahydrofuran at -78 - -35℃;
With dipyridinium dichromate In acetic anhydride
With acetic anhydride In dimethyl sulfoxide at 20℃;
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In dimethyl sulfoxide at 20℃; for 10h;
Stage #1: 1,2-O-isopropylidene-5-O-(t-butyldiphenylsilyl)-α-D-xylofuranose With oxalyl dichloride In dichloromethane; dimethyl sulfoxide at -60℃; for 0.583333h; Inert atmosphere; Stage #2: With triethylamine In dichloromethane; dimethyl sulfoxide at -60 - 20℃; for 3.5h; Inert atmosphere;
With Dess-Martin periodane In dichloromethane at 20℃; Inert atmosphere; 3 Step 3: Into a 20-L 4-necked round-bottom flask, purged and maintained with an inertatmosphere of nitrogen, was placed a solution of (3aR,5R,6S,6aR)-5-[[(tert- butyldiphenylsilyl)oxy]methyl]-2,2-dimethyl-tetrahydro-2H-furo[2,3-d][1,3]dioxol-6-ol (2142 g, 5 mol) in dichloromethane (15 L) and Dess-Martin reagent (3183 g, 7.50 mol) was added. The resulting solution was stirred overnight at room temperature. The reaction was then quenched by the addition of saturated NaHCO3and concentrated under reduced pressure. Et2O was added, and the solid was removed by filtration. The filtrate was concentrated under reduced pressure to provide (3aR,5R,6aS)-5-[[(tert-butyldiphenylsilyl)oxy]methyl]-2,2-dimethyl-tetrahydro-2H- furo[2,3-d][1,3]dioxol-6-one as an oil. The material was used crude without further purification.
Stage #1: 1,2-O-isopropylidene-5-O-(t-butyldiphenylsilyl)-α-D-xylofuranose With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at -60℃; for 0.5h; Stage #2: With triethylamine In dichloromethane at -60 - 20℃; for 3h; 2 second step Add oxalyl chloride (2.8 mL, 30.09 mmol) and anhydrous dichloromethane (40 mL) into a 150 mL two-neck flask, and place the reaction flask in a low temperature tank at -60°C.Slowly add anhydrous dimethyl sulfoxide (4.7mL, 66.17 mmol),The product II was dissolved in dichloromethane (20 mL) and slowly added to the reaction system via a syringe. After the addition was completed, the stirring was continued for 30 min, and then triethylamine (13.8 mL, 99.28 mmol) was added, and the mixture was stirred at -60°C for 1 h. Stir at room temperature for 2h, add water to quench the reaction, extract with dichloromethane (50 mL×2), combine the organic phases, wash with saturated brine (50 mL×1), add anhydrous Na2SO4, dry, filter, and spin dry to obtain the product Go directly to the next step.

Reference: [1]Current Patent Assignee: MERCK & CO INC - WO2015/161137, 2015, A1 Location in patent: Paragraph 00325
[2]Hall, Adrian; Bailey, Patrick D.; Rees, David C.; Rosair, Georgina M.; Wightman, Richard H. [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 3, p. 329 - 343]
[3]Current Patent Assignee: CALITHERA BIOSCIENCES INC - WO2018/119284, 2018, A1 Location in patent: Page/Page column 222; 223
[4]Van Straten, Nicole C.R.; Van Der Marel, Gijsbert A.; Van Boom, Jacques H. [Tetrahedron Letters, 1996, vol. 37, # 20, p. 3599 - 3602]
[5]Van Straten, Nicole C. R.; Van der Marel, Gijsbert A.; Van Boom, Jacques H. [Tetrahedron, 1997, vol. 53, # 18, p. 6509 - 6522]
[6]Hoeffler, Jean-François; Grosdemange-Billiard, Catherine; Rohmer, Michel [Tetrahedron Letters, 2000, vol. 41, # 25, p. 4885 - 4889]
[7]Moon Woo Chun; Myung Jung Kim; Un Hee Jo; Joong Hyup Kim; Kim; Lak Shin Jeong [Nucleosides, nucleotides and nucleic acids, 2001, vol. 20, # 4-7, p. 703 - 706]
[8]Kim, Jaeseung; Weledji, Yvonne N.; Greenberg, Marc M. [Journal of Organic Chemistry, 2004, vol. 69, # 18, p. 6100 - 6104]
[9]Gurjar; Ravindranadh; Karmakar [Chemical Communications, 2001, # 3, p. 241 - 242]
[10]Beahm, Brendan J.; Dehnert, Karen W.; Derr, Nicolas L.; Kuhn, Joachim; Eberhart, Johann K.; Spillmann, Dorothe; Amacher, Sharon L.; Bertozzi, Carolyn R. [Angewandte Chemie - International Edition, 2014, vol. 53, # 13, p. 3347 - 3352][Angew. Chem., 2014, vol. 53, # 13, p. 3347 - 3352,6]
[11]Current Patent Assignee: WAN MRRAY; MERCK & CO INC - WO2020/33285, 2020, A1 Location in patent: Page/Page column 59; 60
[12]Current Patent Assignee: ALI CHEMICAL CHANGZHOU CO LTD - CN112661802, 2021, A Location in patent: Paragraph 0017
  • 7
  • [ 100-39-0 ]
  • [ 114861-14-2 ]
  • [ 213963-74-7 ]
YieldReaction ConditionsOperation in experiment
97.6% With tetrabutyl ammonium fluoride; sodium hydride In tetrahydrofuran; paraffin at 20℃; for 15h;
96% With tetra-(n-butyl)ammonium iodide; sodium hydride In tetrahydrofuran at 20℃; for 12h;
18.56 g With tetra-(n-butyl)ammonium iodide; sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 12h;
  • 8
  • [ 20590-53-8 ]
  • [ 58479-61-1 ]
  • [ 114861-14-2 ]
YieldReaction ConditionsOperation in experiment
99.3% With 1H-imidazole In N,N-dimethyl-formamide at 20℃; for 24h;
  • 9
  • [ 75-15-0 ]
  • [ 114861-14-2 ]
  • [ 74-88-4 ]
  • 5-O-[(1,1-dimethylethyl)diphenylsilyl]-1,2-O-isopropylidene-3-O-[(methylthio)thiocarbonyl]-α-D-xylofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% Stage #1: carbon disulfide; 1,2-O-isopropylidene-5-O-(t-butyldiphenylsilyl)-α-D-xylofuranose With 1H-imidazole; sodium hydride In tetrahydrofuran at 20℃; for 0.5h; Stage #2: methyl iodide In tetrahydrofuran at 20℃; for 0.5h;
  • 10
  • [ 870472-11-0 ]
  • [ 516-12-1 ]
  • [ 114861-14-2 ]
  • 1,2-O-isopropylidene-5-O-tert-butyldiphenylsilyl-3-O-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-α-D-xylofuranose [ No CAS ]
  • 1,2-O-isopropylidene-5-O-tert-butyldiphenylsilyl-3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-α-D-xylofuranose [ No CAS ]
  • N-succinimidyl 2,3,4,6-tetra-O-benzyl-β-D-glucopyranoside [ No CAS ]
YieldReaction ConditionsOperation in experiment
With 2,4,5-tri-tert-butylpyrimidine; 4 A molecular sieve; triethylsilyl trifluoromethyl sulfonate In dichloromethane at 20℃; for 18h;
  • 11
  • [ 870472-11-0 ]
  • [ 114861-14-2 ]
  • 1,2-O-isopropylidene-5-O-tert-butyldiphenylsilyl-3-O-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-α-D-xylofuranose [ No CAS ]
  • 1,2-O-isopropylidene-5-O-tert-butyldiphenylsilyl-3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-α-D-xylofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
With 4 A molecular sieve; dimethyl-(methylthio)-sulphonium trifluoromethanesulphonate In dichloromethane at 20℃; for 26h;
  • 12
  • [ 114861-14-2 ]
  • [ 329365-86-8 ]
  • 1,2-O-isopropylidene-5-O-tert-butyldiphenylsilyl-3-O-(2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)-α-D-xylofuranose [ No CAS ]
  • 1,2-O-isopropylidene-5-O-tert-butyldiphenylsilyl-3-O-(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-α-D-xylofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
With 4 A molecular sieve; dimethyl-(methylthio)-sulphonium trifluoromethanesulphonate In dichloromethane at 20℃; for 27h; Title compound not separated from byproducts;
  • 13
  • [ 114861-14-2 ]
  • C21H28O4Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With triethylsilane; boron trifluoride diethyl etherate In dichloromethane at 20℃; for 2h;
  • 14
  • [ 114861-14-2 ]
  • [ 765942-30-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 7 steps 1.1: acetic anhydride / dimethylsulfoxide / 20 °C 2.1: 6.31 g / NaBH4 / CH2Cl2; methanol / 0.5 h / 0 °C 3.1: 70 percent / TBAF*3H2O / tetrahydrofuran / 1 h / 20 °C 4.1: NaH / tetrahydrofuran / 1 h / 20 °C 4.2: 91.5 percent / tetrahydrofuran / 2 h / Heating 5.1: aq. AcOH / 3.5 h / Heating 5.2: 91.8 percent / NaBH4 / methanol / 20 °C 6.1: 97.6 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 7.1: 92.7 percent / H2 / Pd(OH)2/C / ethyl acetate / 2585.74 Torr
  • 15
  • [ 114861-14-2 ]
  • [ 765942-31-2 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 8 steps 1.1: acetic anhydride / dimethylsulfoxide / 20 °C 2.1: 6.31 g / NaBH4 / CH2Cl2; methanol / 0.5 h / 0 °C 3.1: 70 percent / TBAF*3H2O / tetrahydrofuran / 1 h / 20 °C 4.1: NaH / tetrahydrofuran / 1 h / 20 °C 4.2: 91.5 percent / tetrahydrofuran / 2 h / Heating 5.1: aq. AcOH / 3.5 h / Heating 5.2: 91.8 percent / NaBH4 / methanol / 20 °C 6.1: 97.6 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 7.1: 92.7 percent / H2 / Pd(OH)2/C / ethyl acetate / 2585.74 Torr 8.1: 96.6 percent / pyridine / 6 h / 20 °C
  • 16
  • [ 114861-14-2 ]
  • diisopropyl-phosphoramidous acid 1-[1,2-bis-(<i>tert</i>-butyl-dimethyl-silanyloxy)-ethyl]-3-[bis-(4-methoxy-phenyl)-phenyl-methoxy]-2-(<i>tert</i>-butyl-dimethyl-silanyloxy)-propyl ester 2-cyano-ethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 9 steps 1.1: acetic anhydride / dimethylsulfoxide / 20 °C 2.1: 6.31 g / NaBH4 / CH2Cl2; methanol / 0.5 h / 0 °C 3.1: 70 percent / TBAF*3H2O / tetrahydrofuran / 1 h / 20 °C 4.1: NaH / tetrahydrofuran / 1 h / 20 °C 4.2: 91.5 percent / tetrahydrofuran / 2 h / Heating 5.1: aq. AcOH / 3.5 h / Heating 5.2: 91.8 percent / NaBH4 / methanol / 20 °C 6.1: 97.6 percent / 2,6-lutidine / CH2Cl2 / 1 h / 0 °C 7.1: 92.7 percent / H2 / Pd(OH)2/C / ethyl acetate / 2585.74 Torr 8.1: 96.6 percent / pyridine / 6 h / 20 °C 9.1: 77.8 percent / DIPEA / CH2Cl2 / 5 h / Heating
  • 17
  • [ 114861-14-2 ]
  • [ 37077-81-9 ]
  • 18
  • [ 114861-14-2 ]
  • [ 106799-13-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: NaH; imidazole / tetrahydrofuran / 0.5 h / 20 °C 1.2: 92 percent / tetrahydrofuran / 0.5 h / 20 °C 2.1: 75 percent / (Bu4N)2S2O8; HCO2Na; Na2CO3 / dimethylformamide / 0.25 h / 65 °C
Multi-step reaction with 2 steps 1: 1.) pyridine, (CF3SO2)2O; 2.) n-Bu4NI / 1.) CH2Cl2, -10 deg C, 15 min; 2.) benzene, reflux, 12 h 2: 95 percent / LiEt3BH / tetrahydrofuran / 12 h / Heating
Multi-step reaction with 2 steps 1: 94 percent / pyridine / DMAP / CH2Cl2 / 15 h / 0 °C 2: 77 percent / n-BuSnH / AIBN / toluene / 1 h / 80 °C
Multi-step reaction with 2 steps 1: 94 percent / pyr / DMAP / CH2Cl2 / 15 h / 0 - 25 °C 2: 77 percent / n-Bu3SnH / AlBN / toluene / 1 h / 80 °C
Multi-step reaction with 2 steps 1: 1,2-dichloro-ethane / 2 h / 85 °C 2: tri-n-butyl-tin hydride; 2,2'-azobis(isobutyronitrile) / toluene / 3 h / 116 °C / Inert atmosphere
Multi-step reaction with 3 steps 1: pyridine / dichloromethane 2: tetra-(n-butyl)ammonium iodide / toluene 3: lithium triethylborohydride / tetrahydrofuran

  • 19
  • [ 114861-14-2 ]
  • 5-O-(tert-butyldiphenylsilyl)-3-deoxy-3,3-C-diallyl-1,2-O-isopropylidene-α-D-threo-pentofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: o-iodoxybenzoic acid / dimethylsulfoxide / 10 h / 20 °C 2: benzene / 3 h / 80 °C 3: 60 percent / NaH / dimethylsulfoxide / 3 h / 20 °C 4: 85 percent / DIBAL-H / 0.5 h / -78 °C 5: 90 percent / PPh3; CBr4; pyridine / 0 °C 6: 80 percent / AIBN / benzene / 12 h / 80 °C
  • 20
  • [ 114861-14-2 ]
  • [ 330469-96-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: o-iodoxybenzoic acid / dimethylsulfoxide / 10 h / 20 °C 2: benzene / 3 h / 80 °C
  • 21
  • [ 114861-14-2 ]
  • C27H36O5Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: o-iodoxybenzoic acid / dimethylsulfoxide / 10 h / 20 °C 2: benzene / 3 h / 80 °C 3: 60 percent / NaH / dimethylsulfoxide / 3 h / 20 °C 4: 85 percent / DIBAL-H / 0.5 h / -78 °C
  • 22
  • [ 114861-14-2 ]
  • C27H35BrO4Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: o-iodoxybenzoic acid / dimethylsulfoxide / 10 h / 20 °C 2: benzene / 3 h / 80 °C 3: 60 percent / NaH / dimethylsulfoxide / 3 h / 20 °C 4: 85 percent / DIBAL-H / 0.5 h / -78 °C 5: 90 percent / PPh3; CBr4; pyridine / 0 °C
  • 23
  • [ 114861-14-2 ]
  • C29H38O6Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: o-iodoxybenzoic acid / dimethylsulfoxide / 10 h / 20 °C 2: benzene / 3 h / 80 °C 3: 60 percent / NaH / dimethylsulfoxide / 3 h / 20 °C
  • 24
  • [ 114861-14-2 ]
  • [ 286408-85-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: (COCl)2; TEA; DMSO / tetrahydrofuran / -78 - -35 °C 2: -10 °C
Multi-step reaction with 2 steps 1: Dess-Martin periodane / dichloromethane / 16 h / 0 - 25 °C 2: tetrahydrofuran / 1 h / 25 °C / Inert atmosphere
Multi-step reaction with 2 steps 1: Dess-Martin periodane / dichloromethane / 20 °C / Inert atmosphere 2: tetrahydrofuran / 1 h / 0 - 20 °C / Inert atmosphere
  • 25
  • [ 114861-14-2 ]
  • 3'-amino-3'-deoxyadenosine [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 8 steps 1: pyridine / CH2Cl2 / 0.25 h / -10 °C 2: 56 percent / NaN3 / pyridine / 120 h / Ambient temperature 3: 95 percent / TBAF / tetrahydrofuran / 2 h / Ambient temperature 4: 88 percent / pyridine / 5 h / Ambient temperature 5: 1,) conc. H2SO4, 2.) pyridine, DMAP / 1.) 4 deg C, 6 d, 2.) room temperature, overnight 6: 1.) MSTFA, 2.) TMS-OTf / 1.) DCE, reflux, 30 min, 2.) DCE, 80 deg C, overnight 7: 52 percent / NH3 / tetrahydrofuran / 60 °C 8: 97 percent / H2 / Pd/C / ethanol / 6 h / 760 Torr
  • 26
  • [ 114861-14-2 ]
  • [ 23345-80-4 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: pyridine / CH2Cl2 / 0.25 h / -10 °C 2: 56 percent / NaN3 / pyridine / 120 h / Ambient temperature 3: 95 percent / TBAF / tetrahydrofuran / 2 h / Ambient temperature
Multi-step reaction with 3 steps 1: pyridine / CH2Cl2 / 9 h / Ambient temperature 2: NaN3 / dimethylformamide / 18 h / Ambient temperature 3: tetrabutylammonium fluoride / tetrahydrofuran / 18 h
  • 27
  • [ 114861-14-2 ]
  • [ 216976-56-6 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: pyridine / CH2Cl2 / 0.25 h / -10 °C 2: 56 percent / NaN3 / pyridine / 120 h / Ambient temperature
Multi-step reaction with 2 steps 1: pyridine / CH2Cl2 / 9 h / Ambient temperature 2: NaN3 / dimethylformamide / 18 h / Ambient temperature
Stage #1: 1,2-O-isopropylidene-5-O-(t-butyldiphenylsilyl)-α-D-xylofuranose With pyridine; trifluoromethylsulfonic anhydride Stage #2: With sodium azide In DMF (N,N-dimethyl-formamide)
  • 28
  • [ 114861-14-2 ]
  • [ 190970-11-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: DMSO, Ac2O / 16 h 2: NaBH4 / methanol; CH2Cl2 3: 95 percent / NIS, TfOH / 1,2-dichloro-ethane; diethyl ether / 0.08 h 4: H2, AcOH / Pd/C / propan-2-ol / 16 h / 1810.02 Torr
Multi-step reaction with 3 steps 1: NaBH4 / ethanol 2: 95 percent / NIS, TfOH / CH2Cl2; diethyl ether / 0.08 h 3: H2 / Pd/C
  • 29
  • [ 114861-14-2 ]
  • 2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-4,5-diacetoxy-6-acetoxymethyl-2-[(2R,3S,4R)-2-(tert-butyl-diphenyl-silanyloxymethyl)-4,5-dihydroxy-tetrahydro-furan-3-yloxy]-tetrahydro-pyran-3-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: DMSO, Ac2O / 16 h 2: NaBH4 / methanol; CH2Cl2 3: 95 percent / NIS, TfOH / 1,2-dichloro-ethane; diethyl ether / 0.08 h 4: H2, AcOH / Pd/C / propan-2-ol / 16 h / 1810.02 Torr 5: 76 percent / pyridine / dioxane / 16 h 6: 60 percent / AcOH / H2O / 0.5 h / Heating
Multi-step reaction with 5 steps 1: NaBH4 / ethanol 2: 95 percent / NIS, TfOH / CH2Cl2; diethyl ether / 0.08 h 3: H2 / Pd/C 5: HOAc, ethylene glycol / H2O / Heating
  • 30
  • [ 114861-14-2 ]
  • [ 190970-12-8 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: DMSO, Ac2O / 16 h 2: NaBH4 / methanol; CH2Cl2 3: 95 percent / NIS, TfOH / 1,2-dichloro-ethane; diethyl ether / 0.08 h 4: H2, AcOH / Pd/C / propan-2-ol / 16 h / 1810.02 Torr 5: 76 percent / pyridine / dioxane / 16 h
Multi-step reaction with 4 steps 1: NaBH4 / ethanol 2: 95 percent / NIS, TfOH / CH2Cl2; diethyl ether / 0.08 h 3: H2 / Pd/C
  • 31
  • [ 114861-14-2 ]
  • [ 190970-15-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 8 steps 1: DMSO, Ac2O / 16 h 2: NaBH4 / methanol; CH2Cl2 3: 95 percent / NIS, TfOH / 1,2-dichloro-ethane; diethyl ether / 0.08 h 4: H2, AcOH / Pd/C / propan-2-ol / 16 h / 1810.02 Torr 5: 76 percent / pyridine / dioxane / 16 h 6: 60 percent / AcOH / H2O / 0.5 h / Heating 7: 91 percent / pyridine / 4 h 8: 80 percent / TMSOTf / 1,2-dichloro-ethane / 16 h / Heating
Multi-step reaction with 7 steps 1: NaBH4 / ethanol 2: 95 percent / NIS, TfOH / CH2Cl2; diethyl ether / 0.08 h 3: H2 / Pd/C 5: HOAc, ethylene glycol / H2O / Heating 6: pyridine 7: TMSOTf / CH2Cl2 / Heating
  • 32
  • [ 114861-14-2 ]
  • 2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-4,5-diacetoxy-6-acetoxymethyl-2-[(2R,3R,4R)-4,5-diacetoxy-2-(tert-butyl-diphenyl-silanyloxymethyl)-tetrahydro-furan-3-yloxy]-tetrahydro-pyran-3-yl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 7 steps 1: DMSO, Ac2O / 16 h 2: NaBH4 / methanol; CH2Cl2 3: 95 percent / NIS, TfOH / 1,2-dichloro-ethane; diethyl ether / 0.08 h 4: H2, AcOH / Pd/C / propan-2-ol / 16 h / 1810.02 Torr 5: 76 percent / pyridine / dioxane / 16 h 6: 60 percent / AcOH / H2O / 0.5 h / Heating 7: 91 percent / pyridine / 4 h
  • 33
  • [ 114861-14-2 ]
  • [ 190970-14-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: NaBH4 / ethanol 2: 95 percent / NIS, TfOH / CH2Cl2; diethyl ether / 0.08 h 3: H2 / Pd/C 5: HOAc, ethylene glycol / H2O / Heating 6: pyridine
  • 34
  • [ 114861-14-2 ]
  • [ 86945-40-6 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: pyridine / CH2Cl2 / 9 h / Ambient temperature 2: NaN3 / dimethylformamide / 18 h / Ambient temperature 3: tetrabutylammonium fluoride / tetrahydrofuran / 18 h 4: aq. KMnO4, AcOH, Aliquat 336 / CH2Cl2 / 24 h / Ambient temperature
  • 35
  • [ 114861-14-2 ]
  • [ 86945-41-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: pyridine / CH2Cl2 / 9 h / Ambient temperature 2: NaN3 / dimethylformamide / 18 h / Ambient temperature 3: tetrabutylammonium fluoride / tetrahydrofuran / 18 h 4: aq. KMnO4, AcOH, Aliquat 336 / CH2Cl2 / 24 h / Ambient temperature 5: NaHCO3 / dimethylformamide / 40 h
  • 36
  • [ 114861-14-2 ]
  • 3-deoxy-5-O-<(1,1-dimethylethyl)diphenylsilyl>-α-D-xylofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: 1.) pyridine, (CF3SO2)2O; 2.) n-Bu4NI / 1.) CH2Cl2, -10 deg C, 15 min; 2.) benzene, reflux, 12 h 2: 95 percent / LiEt3BH / tetrahydrofuran / 12 h / Heating 3: BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C
Multi-step reaction with 3 steps 1: 94 percent / pyridine / DMAP / CH2Cl2 / 15 h / 0 °C 2: 77 percent / n-BuSnH / AIBN / toluene / 1 h / 80 °C 3: BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C
  • 37
  • [ 114861-14-2 ]
  • 3-deoxy-5-O-<(1,1-dimethylethyl)diphenylsilyl>-β-D-xylofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: 1.) pyridine, (CF3SO2)2O; 2.) n-Bu4NI / 1.) CH2Cl2, -10 deg C, 15 min; 2.) benzene, reflux, 12 h 2: 95 percent / LiEt3BH / tetrahydrofuran / 12 h / Heating 3: BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C
Multi-step reaction with 3 steps 1: 94 percent / pyridine / DMAP / CH2Cl2 / 15 h / 0 °C 2: 77 percent / n-BuSnH / AIBN / toluene / 1 h / 80 °C 3: BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C
  • 38
  • D-xylofuranose [ No CAS ]
  • [ 114861-14-2 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 50 percent / conc. H2SO4 / 1.) 25 deg C, 6h, 2.) MeOH, 25 deg C, 2h 2: 96 percent / imidazole / dimethylformamide / 2 h / 0 - 25 °C
Multi-step reaction with 2 steps 1: sulfuric acid 2: 1H-imidazole / N,N-dimethyl-formamide
Multi-step reaction with 2 steps 1: sulfuric acid; copper(II) sulfate / 48 h / 20 °C / Inert atmosphere 2: pyridine / 20 °C / Inert atmosphere
  • 39
  • [ 114861-14-2 ]
  • [ 114861-21-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 8 steps 1: 94 percent / pyr / DMAP / CH2Cl2 / 15 h / 0 - 25 °C 2: 77 percent / n-Bu3SnH / AlBN / toluene / 1 h / 80 °C 3: 90 percent / BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C 4: 67 percent / NaH / tetrahydrofuran / 4 h / -30 - 25 °C 5: 90 percent / CSA / 1 h / 25 °C 6: 1.) Sia2BH, 2.) NaOH-H2O2 / 1.) THF, 0 deg C, 1.5h 7: 85 percent / KH / tetrahydrofuran / 14 h / 0 - 25 °C 8: 96 percent / n-Bu4NF / tetrahydrofuran / 4 h / 0 - 25 °C
  • 40
  • [ 114861-14-2 ]
  • [ 106799-15-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 9 steps 1: 94 percent / pyr / DMAP / CH2Cl2 / 15 h / 0 - 25 °C 2: 77 percent / n-Bu3SnH / AlBN / toluene / 1 h / 80 °C 3: 90 percent / BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C 4: 67 percent / NaH / tetrahydrofuran / 4 h / -30 - 25 °C 5: 90 percent / CSA / 1 h / 25 °C 6: 1.) Sia2BH, 2.) NaOH-H2O2 / 1.) THF, 0 deg C, 1.5h 7: 85 percent / KH / tetrahydrofuran / 14 h / 0 - 25 °C 8: 96 percent / n-Bu4NF / tetrahydrofuran / 4 h / 0 - 25 °C 9: 75 percent / SO3*pyr, Et3N / dimethylsulfoxide; CH2Cl2 / 3 h / 25 °C
  • 41
  • [ 114861-14-2 ]
  • [ 106862-35-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 94 percent / pyr / DMAP / CH2Cl2 / 15 h / 0 - 25 °C 2: 77 percent / n-Bu3SnH / AlBN / toluene / 1 h / 80 °C 3: 90 percent / BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C 4: 67 percent / NaH / tetrahydrofuran / 4 h / -30 - 25 °C
  • 42
  • [ 114861-14-2 ]
  • 3-deoxy-5-O-<(1,1-dimethylethyl)diphenylsilyl>-D-xylofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: 94 percent / pyr / DMAP / CH2Cl2 / 15 h / 0 - 25 °C 2: 77 percent / n-Bu3SnH / AlBN / toluene / 1 h / 80 °C 3: 90 percent / BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C
  • 43
  • [ 114861-14-2 ]
  • [ 114861-19-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 94 percent / pyr / DMAP / CH2Cl2 / 15 h / 0 - 25 °C 2: 77 percent / n-Bu3SnH / AlBN / toluene / 1 h / 80 °C 3: 90 percent / BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C 4: 67 percent / NaH / tetrahydrofuran / 4 h / -30 - 25 °C 5: 90 percent / CSA / 1 h / 25 °C
  • 44
  • [ 114861-14-2 ]
  • [ 114861-20-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: 94 percent / pyr / DMAP / CH2Cl2 / 15 h / 0 - 25 °C 2: 77 percent / n-Bu3SnH / AlBN / toluene / 1 h / 80 °C 3: 90 percent / BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C 4: 67 percent / NaH / tetrahydrofuran / 4 h / -30 - 25 °C 5: 90 percent / CSA / 1 h / 25 °C 6: 1.) Sia2BH, 2.) NaOH-H2O2 / 1.) THF, 0 deg C, 1.5h
  • 45
  • [ 114861-14-2 ]
  • [ 106799-14-8 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 7 steps 1: 94 percent / pyr / DMAP / CH2Cl2 / 15 h / 0 - 25 °C 2: 77 percent / n-Bu3SnH / AlBN / toluene / 1 h / 80 °C 3: 90 percent / BCl3 / CH2Cl2; hexane / 0.17 h / -78 °C 4: 67 percent / NaH / tetrahydrofuran / 4 h / -30 - 25 °C 5: 90 percent / CSA / 1 h / 25 °C 6: 1.) Sia2BH, 2.) NaOH-H2O2 / 1.) THF, 0 deg C, 1.5h 7: 85 percent / KH / tetrahydrofuran / 14 h / 0 - 25 °C
  • 46
  • [ 114861-14-2 ]
  • 1,2-O-Isopropylidene-3-O-mesyl-5-O-t-butyldiphenylsilyl-β-D-xylofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
In pyridine; dichloromethane 26 1,2-O-Isopropylidene-3-O-mesyl-5-O-t-butyldiphenylsilyl-β-D-xylofuranose (32, R=Ms). Example 26 1,2-O-Isopropylidene-3-O-mesyl-5-O-t-butyldiphenylsilyl-β-D-xylofuranose (32, R=Ms). Mesyl chloride (17 g, 0.15 mol) is added drop wise to a solution of crude 31 (43 g, 0.1 mol) in pyridine (100 mL), and the mixture is kept standing overnight at room temperature. Crashed ice (1 L) is added to the mixture, and the product is extracted with methylene chloride (300 mL*3). The extracts are combined, washed with water (300 mL*2) and brine (300 mL), dried over sodium sulfate, and concentrated in vacuo to dryness. Traces of pyridine are removed by repeated azeotropic distillation with toluene. The residue is dissolved in methylene chloride (500 mL) and washed with O.IN hydrochloric acid (250 mL*2) and water, dried over sodium sulfate, and concentrated to dryness to give crude 32 (R Ms), 50.1 g (99%). The 1H NMR spectrum of this material is sufficiently pure to be used directly in the next step.
  • 47
  • [ 114861-14-2 ]
  • [ 1101107-70-3 ]
YieldReaction ConditionsOperation in experiment
48% With 1H-imidazole; N-Bromosuccinimide; triphenylphosphine In chlorobenzene for 4h; Reflux;
  • 48
  • [ 58-86-6 ]
  • [ 67-64-1 ]
  • [ 58479-61-1 ]
  • [ 114861-14-2 ]
YieldReaction ConditionsOperation in experiment
Stage #1: D-xylose; acetone With sulfuric acid; copper(II) sulfate at 20℃; Stage #2: With hydrogenchloride In water at 20℃; for 2h; Stage #3: tert-butylchlorodiphenylsilane With pyridine at 0 - 20℃; 1 Preparation of Compound la: [00323] To a stirred solution of (2R, J5',4i?)-2,3,4,5-tetrahydroxypentanal D-xylose (666 mmol) in acetone (2000 mL) were added anhydrous copper(2) sulfate (1139 mmol) and sulfuric acid 95% (10 mL). The reaction mixture was stirred at room temperature overnight, then filtered and neutralized with ammonium hydroxide. After filtration, the mixture was concentrated under reduced pressure. The crude mixture was dissolved in a mixture of water (1750 mL) and concentrated HCI (9 mL) and was stirred at room temperature during 2 hours. The reaction mixture was neutralized by addition of bicarbonate and evaporated to dryness. The crude residue was dissolved with dichloromethane and the organic layer was dried on Na2S04, filtered and concentrated under reduced pressure. The crude mixture was dissolved in anhydrous pyridine (1200 mL) and tert-butylchlorodiphenylsilane (679 mmol) was added at 0°C. The reaction mixture was stirred at room temperature overnight. Methanol (20 mL) was added and the mixture was concentrated under reduced pressure. The organic layer was washed successively with HC1 0.5N, a saturated aqueous solution of NaHC03 and brine, dried over Na2S04 and concentrated under reduced pressure to give the expected crude compound in 69% yield. 1H NMR (CDC13, 400MHz) δ (ppm) 1.05 (s, 9H), 1.33 (s, 3H), 1.47 (s, 3H), 4.03 (brs, 1H), 4.1-4.15 (m, 3H), 4.37 (brs, 1H), 4.55 (d, J= 3.67Hz, 1H), 6 (d, J= 3.67Hz, 1H), 7.38-7.47 (m, 6H), 7.66-7.72 (m, 4H).
  • 49
  • [ 114861-14-2 ]
  • [ 4301-14-8 ]
  • (3aR,5R,6R,6aR)-5-(((tert-butyldiphenylsilyl)oxy)methyl)-6-ethynyl-2,2-dimethyl-tetrahydrofuro[2,3 -d][1,3]dioxol-6-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% Stage #1: 1,2-O-isopropylidene-5-O-(t-butyldiphenylsilyl)-α-D-xylofuranose With acetic anhydride In dimethyl sulfoxide at 20℃; for 48h; Inert atmosphere; Stage #2: acetylenemagnesium bromide In tetrahydrofuran; dimethyl sulfoxide at 20℃; Inert atmosphere; Cooling with ice; Synthesis of 1,2-O-isopropylidene-3-C-ethynyl-5-O-TBDPS-α-D-ribofuranose (II) I (18 g, 42 mmol) was dissolved in anhydrous DMSO (130 mL) under argon. Next, Ac2O (15.88 mL, 168 mmol) was added and the resulting solution stirred at rt for 2 days. Then, the mixture was poured into ice water (200 mL) and EA (400 mL). The layers were separated and the organic layer sequentially washed with sat. NaHCO3 sol. (200 mL) and brine (150 mL). The organic layer was dried over Na2SO4, filtered and evaporated till dry. The oily residue was co-evaporated with toluene (3 x 40 mL). Next, the residue was re-dissolved in anhydrous THF (125 mL) under argon and cooled in an ice bath. Subsequently, ethynylMgBr (0.5 M in THF; 100 mL, 50 mmol) was added dropwise via an addition funnel. After complete addition the mixture was allowed to warm to rt, after which TLC (25 % EA / Hex, Rf= 0.39) showed full conversion of the intermediate ketone. The mixture wasquenched by adding sat. NH4Cl sol. (50 mL). Next, the mixture was extracted with EA (300 mL) andwater (100 mL). The layers were separated and the water layer extracted with EA (2 x 100 mL). Organiclayers were combined, dried over Na2SO4, filtered and evaporated till dry. The residue was coevaporated with Celite and purified by column chromatography (10 % → 25 % EA / Hex) to give awaxy white solid (16.23 g, 35.85 mmol) in 85 % yield.
  • 50
  • [ 124-63-0 ]
  • [ 114861-14-2 ]
  • 1,2-O-isopropylidene-3-O-mesyl-5-O-t-butyldiphenylsilyl-α-D-xylofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
With pyridine at 20℃; 26 1,2-O-isopropylidene-3-O-mesyl-5-O-t-butyldiphenylsilyl-α-D-xylofuranose (32, R=Ms) mesyl chloride (17 g, 0.15 mol) is added drop wise to a solution of crude 31 (43 g, 0.1 mol) in pyridine (100 mL), and the mixture is kept standing overnight at room temperature. Crashed ice (1 L) is added to the mixture, and the product is extracted with methylene chloride (300 mL*3). The extracts are combined, washed with water (300 mL*2) and brine (300 mL), dried over sodium sulfate, and concentrated in vacuo to dryness. Traces of pyridine are removed by repeated azeotropic distillation with toluene. The residue is dissolved in methylene chloride (500 mL) and washed with 0.1N hydrochloric acid (250 mL*2) and water, dried over sodium sulfate, and concentrated to dryness to give crude 32 (R=Ms), 50.1 g (99%). The 1H NMR spectrum of this material is sufficiently pure to be used directly in the next step.
  • 51
  • [ 114861-14-2 ]
  • [ 6160-65-2 ]
  • 5-O-tert-Butyl(diphenyl)silyl-1,2-O-isopropylidene-3-thiocarbonylimidazolo-D-xylofuranose [ No CAS ]
YieldReaction ConditionsOperation in experiment
63% In 1,2-dichloro-ethane at 85℃; for 2h;
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