Name: 14215-97-5|(3R,4R,5R)-2-Acetoxy-5-((benzoyloxy)methyl)tetrahydrofuran-3,4-diyl dibenzoate|98%
Brand: Ambeed
SKU: A278389
Price: 7.0 USD
Availability: InStock
Rating: 97 (25 reviews)

1
[ 6974-32-9 ]
[ 555-30-6 ]
[ 79439-78-4 ]
[ 6988-74-5 ]
[ 14215-97-5 ]

Reference： [1]European Journal of Medicinal Chemistry,1981,vol. 16,p. 219 - 227

2
[ 41799-71-7 ]
[ 14215-97-5 ]
[ 109986-84-7 ]

Reference： [1]Journal of Heterocyclic Chemistry,1986,vol. 23,p. 1777 - 1779

3
[ 7355-55-7 ]
[ 14215-97-5 ]
2-amino-6-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-7H-pyrrolo<2,3-d>pyrimidin-4(3H)-one [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1990,vol. 33,p. 2750 - 2755

4
[ 65996-50-1 ]
[ 14215-97-5 ]
[ 142544-99-8 ]

Reference： [1]Journal of Heterocyclic Chemistry,1992,vol. 29,p. 343 - 354

5
[ 16233-51-5 ]
[ 14215-97-5 ]
[ 153085-38-2 ]

Reference： [1]Nucleosides and Nucleotides,1994,vol. 13,p. 925 - 937

6
[ 62981-82-2 ]
[ 14215-97-5 ]
2-amino-6-methyl-5-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-7H-pyrrolo<2,3-d>pyrimidin-4(3H)-one [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1990,vol. 33,p. 2750 - 2755

7
[ 5387-84-8 ]
[ 14215-97-5 ]
[ 90914-33-3 ]

Reference： [1]Journal of Medicinal Chemistry,1984,vol. 27,p. 1119 - 1127

8
[ 65996-58-9 ]
[ 14215-97-5 ]
[ 864155-80-6 ]

Reference： [1]Journal of Medicinal Chemistry,1990,vol. 33,p. 2750 - 2755

9
[ 54738-73-7 ]
[ 14215-97-5 ]
[ 90914-30-0 ]

Reference： [1]Journal of Medicinal Chemistry,1984,vol. 27,p. 1119 - 1127

10
[ 30161-97-8 ]
[ 14215-97-5 ]
[ 122970-39-2 ]

Yield	Reaction Conditions	Operation in experiment
	With pyridine; ammonium sulfate; 1,1,1,3,3,3-hexamethyl-disilazane; In ethyl acetate; acetonitrile;	EXAMPLE 1 5-amino-3-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)thiazolo-[4,5-d]pyrimidine-2,7(6H)-dione (6) A mixture of dry 5-aminothiazolo[4,5-d]pyrimidine-2,7-(3H,6H)-dione 4 (5.5 g, 30 mmol), hexamethyldisilazane (HMDS, 100 mL), ammonium sulfate (15 mg) and pyridine (10 mL) was heated under reflux for 4 h with the exclusion of moisture. Excess HMDS was removed by distillation to provide the syrupy bis-silyl derivative. The bis-silyl intermediate was dissolved in dry acetonitrile (300 mL) and <strong>[14215-97-5]1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose</strong> (5: 15.1 g, 30 mmol) was added followed by trimethlsilyl trifluoromethanesufonate (9.3 mL, 42 mmol). The clear reaction mixture was stirred at ambient temperature for 16 h. The solvent was evaporated to dryness and the residual syrup was dissolved in EtOAc (600 mL). The solution was washed with 5% NaHCO3 solution (2*150 mL), and the dried (Na2 SO4) organic layer was evaporated. The residual syrup was triturated with ether to yield 18.1 g (96%). The resulting foam was purified on a silica gel column by Prep LC techniques using CHCl3 -MeOH (9:1, v/v) as the solvent.
	With pyridine; ammonium sulfate; 1,1,1,3,3,3-hexamethyl-disilazane; In ethyl acetate; acetonitrile;	EXAMPLE 1 5-amino-3-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)thiazolo[4,5-d]pyrimidine-2,7(6H)-dione (6) A mixture of dry 5-aminothiazolo[4,5-d]pyrimidine-2,7(3H,6H)-dione 4 (5.5 g, 30 mmol), hexamethyldisilazane (HMDS, 100 mL), ammonium sulfate (15 mg) and pyridine (10 mL) was heated under reflux for 4 h with the exclusion of moisture. Excess HMDS was removed by distillation to provide the syrupy bis-silyl derivative. The bis-silyl intermediate was dissolved in dry acetonitrile (300 mL) and <strong>[14215-97-5]1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose</strong> (5: 15.1 g, 30 mmol) was added followed by trimethylsilyl trifluoromethanesufonate (9.3 mL, 42 mmol). The clear reaction mixture was stirred at ambient temperature for 16 h. The solvent was evaporated to dryness and the residual syrup was dissolved in EtOAc (600 mL). The solution was washed with 5% NaHCO3 solution (2*150 mL), and the dried (Na2 SO4) organic layer was evaporated. The residual syrup was triturated with ether to yield 18.1 g (96%). The resulting foam was purified on a silica gel column by Prep LC techniques using CHCl3 --MeOH (9:1, v/v) as the solvent.

Reference： [1]Journal of Medicinal Chemistry,1990,vol. 33,p. 407 - 415
[2]Patent: US5041426,1991,A
[3]Patent: US4880784,1989,A

11
[ 41761-37-9 ]
[ 14215-97-5 ]
2-amino-5-methyl-7-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-5H-pyrrolo<3,2-d>pyrimidin-4(3H)-one [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1990,vol. 33,p. 2750 - 2755

12
[ 129872-87-3 ]
[ 14215-97-5 ]
2-amino-5-ethyl-7-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-5H-pyrrolo<3,2-d>pyrimidin-4(3H)-one [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1990,vol. 33,p. 2750 - 2755

13
[ 129872-88-4 ]
[ 14215-97-5 ]
2-amino-5-benzyl-7-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-5H-pyrrolo<3,2-d>pyrimidin-4(3H)-one [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1990,vol. 33,p. 2750 - 2755

14
[ 88474-32-2 ]
[ 14215-97-5 ]
[ 95245-17-3 ]

Reference： [1]Chemistry of Heterocyclic Compounds,1984,vol. 20,p. 1287 - 1294
Khimiya Geterotsiklicheskikh Soedinenii,1984,p. 1556 - 1564

15
[ 73236-43-8 ]
[ 14215-97-5 ]
[ 80822-31-7 ]

Reference： [1]Journal of Organic Chemistry,1982,vol. 47,p. 1769 - 1772

16
[ 80822-28-2 ]
[ 14215-97-5 ]
[ 80822-32-8 ]

Reference： [1]Journal of Organic Chemistry,1982,vol. 47,p. 1769 - 1772

17
[ 83255-86-1 ]
[ 14215-97-5 ]
[ 90914-43-5 ]

Reference： [1]Journal of Medicinal Chemistry,1984,vol. 27,p. 1119 - 1127

18
[ 97151-21-8 ]
[ 14215-97-5 ]
[ 97151-22-9 ]

Reference： [1]Journal of Medicinal Chemistry,1985,vol. 28,p. 1198 - 1203

19
[ 151266-23-8 ]
[ 14215-97-5 ]
(2R,3R,4R,5R)-2-(4-amino-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-1-yl)-5-((benzoyloxy)methyl)tetrahydrofuran-3,4-diyl dibenzoate [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1993,vol. 36,p. 3424 - 3430

20
[ 1122-28-7 ]
[ 14215-97-5 ]
[ 94619-73-5 ]

Reference： [1]Nucleosides and Nucleotides,1994,vol. 13,p. 2307 - 2320

21
[ 14215-97-5 ]
[ 52522-97-1 ]
[ 23392-16-7 ]

Reference： [1]Synthesis,1995,p. 1465 - 1479

22
[ 5451-40-1 ]
[ 14215-97-5 ]
[ 15373-23-6 ]

Reference： [1]Collection of Czechoslovak Chemical Communications,2002,vol. 67,p. 325 - 335
[2]Bioorganic and Medicinal Chemistry Letters,2000,vol. 10,p. 403 - 406

23
[ 93-14-1 ]
[ 14215-97-5 ]
[ 664994-56-3 ]

Reference： [1]Synthesis,2003,p. 2378 - 2384

24
[ 21901-41-7 ]
[ 14215-97-5 ]
[ 866826-70-2 ]

Reference： [1]Journal of Medicinal Chemistry,2005,vol. 48,p. 6454 - 6460

25
[ 2004-03-7 ]
[ 14215-97-5 ]
[ 14985-78-5 ]

Reference： [1]Molecules,2005,vol. 10,p. 1015 - 1020

26
4-chloro-5,6-dimethyl-7<i>H</i>-pyrrolo[2,3-<i>d</i>]pyrimidin-2-ylamine [ No CAS ]
[ 14215-97-5 ]
4-chloro-5,6-dimethyl-2-[(2,3,5-tri-O-benzoyl)-β-D-ribofuranosyl]amino-7H-pyrrolo[2,3-d]pyrimidine [ No CAS ]
4-chloro-5,6-dimethyl-2-N,N-bis[(2,3,5-tri-O-benzoyl)-β-D-ribofuranosyl]amino}-7H-pyrrolo[2,3-d]pyrimidine [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2006,vol. 71,p. 81 - 90

27
[ 14215-97-5 ]
[ 224946-82-1 ]
[ 864155-79-3 ]

Reference： [1]Nucleosides, nucleotides and nucleic acids,2005,vol. 24,p. 45 - 62

28
[ 55864-87-4 ]
[ 57-13-6 ]
[ 14215-97-5 ]
[ 74-88-4 ]
[ 565432-23-7 ]
[ 565432-22-6 ]

Reference： [1]Nucleosides, nucleotides and nucleic acids,2005,vol. 24,p. 1947 - 1970

29
[ 14215-97-5 ]
[ 1198-83-0 ]
[ 51549-17-8 ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 14302 - 14303

30
[ 2022-85-7 ]
[ 14215-97-5 ]
[ 53294-73-8 ]

Reference： [1]Journal of the American Chemical Society,2006,vol. 128,p. 4172 - 4173

31
[ 945738-71-6 ]
[ 14215-97-5 ]
[ 945738-72-7 ]

Reference： [1]Nucleosides, nucleotides and nucleic acids,2006,vol. 25,p. 1391 - 1397

32
[ 952022-77-4 ]
[ 14215-97-5 ]
[ 952022-78-5 ]

Yield	Reaction Conditions	Operation in experiment
40%		6-[(lE)-(dimethylamino)methylene]amino}-2-(pentylthio)-9-(2,3,5-tri-O-benzoyl-beta-D- ribofuranosyl)-9H-purin- 8 -ol <n="70"/>iV-[8-hydroxy-2-(pentylthio)-9H-purin-6-yl]-N,N-dimethyliniidofonnamide (150 mg, 0.48 mmol) was dissolved in acetonitrile (10 niL) at rt, followed by addition of l-O-acetyl-2,3,5- tri-0-benzoyl-D-ribofuranose (1 g, 4.56 eq), andN,N-bis(trimethylsilyl)acetamide (1 mL, 8.9 eq). After stirring for 30 min at 60 0C the reaction was cooled to rt, followed by the addition of neat tin (IV) chloride (0.6 mL, 6.6 eq). The reaction was then heated to 65 0C overnight under nitrogen. The reaction was then cooled to rt and concentrated in vacuo. The crude reaction was resuspended in dichloromethane (50 mL) and washed by saturated sodium bicarbonate (2 X 200 mL) and brine (2 X 200 mL). The organic portions were then dried over magnesium sulfate, filtered and concentrated in vacuo. The crude product was purified by RP- etaPLC. Yield 150 mg (40%). MS(APCI-pos^) obs M+eta (at) 753.3 amu

Reference： [1]Patent: WO2007/113538,2007,A1 .Location in patent: Page/Page column 68-69

33
C₉H₁₃NO₃Si [ No CAS ]
[ 14215-97-5 ]
[ 960359-45-9 ]

Yield	Reaction Conditions	Operation in experiment
52%	With tin(IV) chloride; In acetonitrile; for 2h;Heating / reflux;	The condensation mixture was refluxed for 2 hours and 2 major compounds 2 and 3 were isolated. This reaction was described in the ribo series using either TMSOTf or tin chloride as coupling reagents [Nucleosides, Nucleotides & Nucleic acids 2001, 20 (4-7), 731; Nucleosides & Nucleotides, 1991, 10 (6), 1333]. Deprotections of 2 and 3 were quantitative and led respectively to products 4 and 5j which were purified and recrystallized.

Reference： [1]Patent: WO2007/144686,2007,A1 .Location in patent: Page/Page column 130

34
[ 10128-91-3 ]
[ 14215-97-5 ]
[ 960359-48-2 ]

Yield	Reaction Conditions	Operation in experiment
74%	With 1,8-diazabicyclo[5.4.0]undec-7-ene; In acetonitrile;	Acidic treatment [J.AC.S. 1947, 69, 1034-37] of 2-hydroxynicotinic acid led quantitatively to the base _ (pyridin^-one-S-carboxylic acid methyl ester) which was condensed with acylated sugar in presence of diazabicyclo[5.4.0]undec-7-ene to give 2 and 3. Ammoniacal treatment at room temperature afforded the 2- pyrimidinone carboxylic acid methyl esters 4 and 5, while similar treatment at 1000C led to the pyrimidinone carboxamide derivatives 6 and 7. AU compounds have been characterized. Physical data of 6 is in accordance with data from literature [J. Heterocyclic Chem. 1989, 26, 1835] and a NOE experiment confirmed the beta- anomery.

Reference： [1]Patent: WO2007/144686,2007,A1 .Location in patent: Page/Page column 130-131

35
C₈H₁₃N₃O₂Si [ No CAS ]
[ 14215-97-5 ]
[ 960359-53-9 ]

Yield	Reaction Conditions	Operation in experiment
40%	With tin(IV) chloride; In acetonitrile; for 2h;Heating / reflux;	Condensation of silylated 4-hydroxy-5-pyrimidinecarboxamide with acylated sugar in presence of tin chloride in acetonitrile led to a mixture of 4 compounds. Compound 2 was isolated as the major product and deprotected to give the pyrimidinone carboxamide nucleoside analog 4.

Reference： [1]Patent: WO2007/144686,2007,A1 .Location in patent: Page/Page column 131

36
[ 149765-16-2 ]
[ 14215-97-5 ]
[ 873792-67-7 ]

Reference： [1]Nucleosides, nucleotides and nucleic acids,2007,vol. 26,p. 603 - 606
[2]Angewandte Chemie - International Edition,2007,vol. 46,p. 2325 - 2327

37
[ 14215-97-5 ]
[ 5413-80-9 ]
1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-1H-pyrazolo[3,4-d]pyrimidine-4,6-diamine [ No CAS ]
2-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6-diamine [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2007,vol. 5,p. 3034 - 3045

38
[ 637338-77-3 ]
[ 14215-97-5 ]
3-chloro-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-1H-pyrazolo[3,4-d]pyrimidine-4,6-diamine [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2007,vol. 5,p. 3034 - 3045

39
[ 144750-82-3 ]
[ 14215-97-5 ]
[ 908143-17-9 ]

Reference： [1]Organic and Biomolecular Chemistry,2007,vol. 5,p. 3034 - 3045

40
[ 398117-44-7 ]
[ 14215-97-5 ]
[ 908143-18-0 ]

Reference： [1]Organic and Biomolecular Chemistry,2007,vol. 5,p. 3034 - 3045

41
[ 14215-97-5 ]
[ 183274-49-9 ]
6-amino-4-isopropoxy-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-1H-pyrazolo[3,4-d]pyrimidine [ No CAS ]
6-amino-4-isopropoxy-2-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-2H-pyrazolo[3,4-d]pyrimidine [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2007,vol. 5,p. 3034 - 3045

42
[ 14215-97-5 ]
[ 2341-22-2 ]

Reference： [1]Journal of the American Chemical Society,2006,vol. 128,p. 4172 - 4173

43
[ 14215-97-5 ]
[ 70255-65-1 ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 14302 - 14303

44
[ 14215-97-5 ]
[ 4105-39-9 ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 14302 - 14303

45
[ 14215-97-5 ]
[ 445417-49-2 ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 14302 - 14303

46
[ 14215-97-5 ]
N-[[9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-2-methylthiopurin-6-yl]carbamoyl]-L-threonine [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 14302 - 14303

47
[ 14215-97-5 ]
N-[[9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)-2-methylthiopurin-6-yl]carbamoyl]-O-tert-butyldimethylsilyl-L-threonine [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 14302 - 14303

48
[ 14215-97-5 ]
N-[[9-(β-D-ribofuranosyl)-2-methylthiopurin-6-yl]carbamoyl]-O-tert-butyldimethylsilyl-L-threonine trimethylsilylethyl ester [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 14302 - 14303

49
[ 14215-97-5 ]
[ 3056-17-5 ]

Reference： [1]Journal of Organic Chemistry,1989,vol. 54,p. 4780 - 4785
[2]Journal of Organic Chemistry,1989,vol. 54,p. 4780 - 4785
[3]Journal of Organic Chemistry,1989,vol. 54,p. 4780 - 4785

50
[ 220553-80-0 ]
[ 14215-97-5 ]
[ 220553-99-1 ]

Yield	Reaction Conditions	Operation in experiment
0.65 g (56%)	With pyridine; ammonium sulfate; tin(IV) chloride; In methanol; dichloromethane; 1,2-dichloro-ethane; 1,1,1,3,3,3-hexamethyl-disilazane;	Preparation of 7-Amino-1-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)-1,3-aza-phospholo[4,5-d]pyrimidine [compound 21, R=2,3,5-tri-O-benzoyl-beta-D-ribofuranose] A mixture of 7-amino-1H-1,3-azaphospholo[4,5-d]pyrimidine (compound 10, 0.3 g, 1.97 mmol) in 1,1,1,3,3,3-hexamethyldisilazane (HMDS, 5 mL), pyridine (5 mL) and ammonium sulfate (50 mg) was heated under reflux for 18 h. The reaction mixture was allowed to cool to room temperature and the excess of HMDS and pyridine were evaporated in vacuo. The silyl derivative of compound 10 was dried under high vacuum for 3 h. The dried material was dissolved in 1,2-dichloroethane (30 mL) to which <strong>[14215-97-5]1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose</strong> (1.28 g, 2.4 mmol) was added. The mixture was cooled in an ice bath. A solution of SnCl4 in dichloromethane (1 M, 2.8 mL, 2.8 mmol) was added keeping the flask under an argon atmosphere. After stirring the mixture in the ice bath for 4 h, the ice bath was removed and the reaction was continued at ambient temperature for 18 h. Methanol (10 mL) was added and after 10 min it was diluted with dichloromethane (100 mLL). The organic layer was washed with saturated sodium hydrogen carbonate solution (50 mL) and the resultant emulsion was filtered through a Celite pad. Organic layer was separated and the aqueous layer was extracted with dichloromethane (2*50 mL). The combined organic layer was dried (Na2 SO4) and evaporated. The solid thus obtained was crystallized from a mixture of ethyl acetate and methanol to give 0.65 g (56%) of the title compound, mp 248-250 C. (dec). 1 H nmr (DMSO-d6): delta 4.85(m,2 t C5 H2), 4.96 (m, 1 H, C4' H), 6.01 (m, 1 H, C3' H), 6.19 (m, 1 H, C2' H), 6.51 (d, 1 H, C1' H), 7.44-8.05 (m, 15 H, 3Bz), 8.44 and 8.47 (2s, 2 H, NH2), 8.75 (d, 1 H, C5 H), and 8.95 (d, 1 H, J =57 Hz, C2 H). Anal. Calcd. for C31 H25 N4 O7 P.0.5 H2 O: C, 61.49; H, 4.33; N, 9.25. Found: C, 61.61; H, 3.88; N, 9.21.

Reference： [1]Patent: US6069132,2000,A

51
2,6-dichloro-9(H)-purine [ No CAS ]
[ 14215-97-5 ]
[ 15373-23-6 ]

Yield	Reaction Conditions	Operation in experiment
87%	In dichloromethane;	9-(2,3,5-Tri-O-benzoyl-beta-D-ribofuranosyl)-2,6-dichloro-9H-purine 2,6-dichloro-9(H)-purine (5.8 g, 30.7 mmol) and 1-0-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose (16.26 g, 32.2 mmol) were thoroughly mixed (as powdery solids) and fused together at 145-150 C. under oil pump vacuum. The resultant oily mixture was stirred gently for 0.75 h (during which time the acetic acid by-product evaporated) and cooled to ca. 50 C. before being dissolved in dichloromethane (100 ml) with stirring. This solution was applied directly to a column of silica gel (6*22 cm) and eluted initially with cyclohexane/dichloromethane (1/1), then with dichioromethane and finally with cyclohexane/ethyl acetate (1/1) to provide 9-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)-2,6-dichloro-9H-purine (16.6 g, 87%) as a colourless foam, TLC rf 0.50 [SiO2, cyclohexane/ethyl acetate (1/1)]. 1 H NMR (DMSO-d6) gamma 4.72 (1 H, dd, H-5'a), 4.88 (1H, q, H-4'), 4.93 (1H, dd, H-5'b), 6.15 (2H, m, H-2' & H-3'), 6.50 (1H, d, H-1'), 7.34-7.65 (9H, m, m- & p-ArH), 7.90-8.13 (6H, m, o-ArH), 8.28 (1H, s, H-8). (This method of preparation is a modification of that described by Imai, K-i. et al, Chemical and Pharmaceutical Bulletin, 1966, 14, 1377-1381, but without the use of a catalyst).

Reference： [1]Patent: US5430027,1995,A

52
[ 40316-88-9 ]
[ 14215-97-5 ]
(S)-(-)-3-(1-methyl-2-pyrrolidinyl)-2-pyridone-N-β-D-ribofuranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tin(IV) chloride; In dichloromethane; 1,2-dichloro-ethane;	After completion of the reaction, the reaction mixture was concentrated under reduced pressure, thereby obtaining a trimethylsilyl derivative of the compound (2a) in oil state. This derivative was dissolved in 20 ml of 1,2-dichloroethane, to which 6.0 g of commercially available 2,3,5-tri-O-benzoyl-1-O-acetylribofuranose (5a) was added. Further, 12 ml of 1 M tin tetrachloride was added thereto, and the mixture was reacted for 5 hours. After 40 ml of dichloromethane was added to the reaction mixture, the reaction mixture was neutralized with 1 N sodium hydroxide. An organic layer was separated and washed with water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by means of silica gel column chromatography using ethyl acetate as a developing solvent, thereby obtaining 6.1 g of (S)-(-)-3-(1-methyl-2-pyrrolidinyl)-2-pyridone-2,3,5-tri-O-benzoyl-N-beta-D-ribofuranoside (6a) in white solid form.

Reference： [1]Patent: EP628567,1994,A1

53
[ 7677-24-9 ]
[ 14215-97-5 ]
[ 23316-67-8 ]

Reference： [1]Chemical Communications,2006,p. 2720 - 2721

54
[ 931-86-2 ]
[ 14215-97-5 ]
[ 320-67-2 ]

Yield	Reaction Conditions	Operation in experiment
		34.7 mL of BSTFA are added to a suspension of 6.3 g of azacytosine in 126 mL of dichloromethane. The mixture is brought to reflux temperature and it is stirred for 90 minutes. 11.35 mL of trimethylsilyltriflate and then a solution of 16.7 g of 1,2,3,5-tetra-O-acetyl-D-ribofuranose in 33 mL of dichloromethane are added to the limpid solution, in about ten minutes. Reflux and stirring are maintained for two hours, it is cooled to room temperature, 250 mL of methanol are added controlling the temperature in an ice bath. Concentration is carried out at low pressure until a residue volume of about 150 mL is obtained, 250 mL of methanol, are added and once again concentration is carried out at low pressure until a residue volume of about 150 mL is obtained. 200 mL of methanol are added, it is heated to 50C and 48 mL of a 10% solution of sodium methylate in methanol are added. It is stirred for 1 hour, it is cooled to room temperature, it is stirred to complete precipitation and the solid is filtered by washing it on the filter with methanol. 9.9 g of azacitidine with HPLC purity (UV 254 nm) of 98.9% are obtained after drying at low pressure. After recrystallisation from methanol-dimethyl sulfoxide the HPLC purity (UV 254 nm) is of 99.7%.
		Example 7 Preparation of Azacitidine 34.7 mL of BSTFA are added to a suspension of 6.3 g of azacytosine in 126 mL of dichloromethane. The mixture is brought to reflux temperature and it is stirred for 90 minutes. 11.35 mL of trimethylsilyltriflate and then a solution of 29 g of 2,3,5-tri-O-benzoyl-1-O-acetyl-D-ribofuranose in 50 mL of dichloromethane are added to the limpid solution, in about ten minutes. Reflux and stirring are maintained for two hours, it is cooled to room temperature and the reaction mixture is poured onto 250 mL of methanol controlling the temperature in an ice bath. Concentration is carried out at low pressure until a residue volume of about 150 mL is obtained, 250 mL of methanol are added and once again concentration is carried out at low pressure until a residue volume of about 150 mL is obtained. 200 mL of methanol are added, it is heated to 50 C. and 48 mL of a 10% solution of sodium methylate in methanol are added. It is stirred for 1 hour, it is cooled to room temperature, it is stirred to complete precipitation and the solid is filtered by washing it on the filter with methanol. 9.3 g of azacitidine with HPLC purity (UV 254 nm) of 91.6% are obtained after drying at low pressure.

Reference： [1]Patent: EP2371825,2011,A1 .Location in patent: Page/Page column 9
[2]Patent: US2011/245485,2011,A1 .Location in patent: Page/Page column 6

55
[ 156270-70-1 ]
[ 14215-97-5 ]
[ 1417534-84-9 ]

Reference： [1]ChemPhysChem,2012,vol. 13,p. 3350 - 3356

56
[ 14215-97-5 ]
[ 942-44-9 ]
[ 1417534-85-0 ]

Reference： [1]ChemPhysChem,2012,vol. 13,p. 3350 - 3356

57
[ 67410-64-4 ]
[ 14215-97-5 ]
[ 67410-59-7 ]

Yield	Reaction Conditions	Operation in experiment
56%		A mixture of 2 (7.55 g, 50 mmol), freshly distilled hexamethyldisilazane (38 mL), and a few crystals of ammonium sulfate (50 mg) was heated at reflux temperature for 15 h with the exclusion of moisture. The excess hexamethyldisilazane was removed by distillation and the residual gum was dissolved in anhydrous 1,2-dichloroethane (250 mL). To the solution was added compound 1 (25.22 g, 50 mmol) followed by stannic chloride (17.5 g, 67.5 mmol). The reaction mixture was protected from moisture and stirred for 30 h at room temperature. The brown solution was then poured into 500 mL of chloroform and the resulting emulsion was filtered through Celite. The filtrate was washed with water, dried over anhydrous sodium sulfate and evaporated. The residue was purified by column chromatography (silica gel, ethyl acetate:water:1-propanol=4:2:1, v/v, upper phase) to give a light yellow solid. (17.0 g, 56%).

Reference： [1]Patent: US8389703,2013,B1 .Location in patent: Page/Page column 15

58
4-amino-6-bromo-5-cyano-1H-pyrrolo[2,3-d]pyrimidine [ No CAS ]
[ 14215-97-5 ]
[ 151707-53-8 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 3385 - 3388

59
[ 14215-97-5 ]
[ 10310-21-1 ]
[ 3387-63-1 ]

Yield	Reaction Conditions	Operation in experiment
73%		To a mixture of pre-silylated 6-Cl-guanine (usingand (NH4)2S04) (25.2 g, 150 mmol) in DCE (300mE) was added 30-1 (50 g, 100 mmol) and TMSOTf (33.3 g,150 mmol) at 0 C. The mixture was stirred at 70 C. for 16 h, and then concentrated at low pressure. The residue was reHMDSdissolved in EA, and washed with sat. aq. NaHCO3 and brine.The organic layer was dried over anhydrous Na2SO4, andconcentrated at low pressure. The residue was purified on silica gel colunm (PE/EA=2/1) to give pure 30-2 (45 g, 73%) as a white solid.
45 g		To a mixture of pre-silylated 6-Cl-guanine (using HMDS and (NH4)2SO4) (25.2 g, 150 mmol) in DCE (300 mL) was added 40-1 (50 g, 100 mmol) and TMSOTf (33.3 g, 150 mmol) at 0 C. The mixture was stirred at 70 C. for 16 h, and then concentrated at low pressure. The residue was re-dissolved in EA, and washed with sat. aq. NaHCO3 and brine. The organic layer was dried over anhydrous Na2SO4, and concentrated at low pressure. The residue was purified on silica gel column (PE/EA=2/1) to give pure 40-2 (45 g, 73%) as a white solid.

Reference： [1]Patent: US2015/366888,2015,A1 .Location in patent: Paragraph 0400; 0401
[2]Patent: US2014/179627,2014,A1 .Location in patent: Paragraph 0338

60
[ 14215-97-5 ]
pre-silylated 6-Cl-guanine [ No CAS ]
[ 3387-63-1 ]

Yield	Reaction Conditions	Operation in experiment
73%	With trimethylsilyl trifluoromethanesulfonate; In 1,2-dichloro-ethane; at 0 - 70℃; for 16h;	To a mixture of pre-silylated 6-Cl-guanine (using HMDS and (NH4)2SO4) (25.2 g, 150 mmol) in DCE (300 mL) was added 30-1 (50 g, 100 mmol) and TMSOTf (33.3 g, 150 mmol) at 0 C. The mixture was stirred at 70 C. for 16 h, and then concentrated at low pressure. The residue was re-dissolved in EA, and washed with sat. aq. NaHCO3 and brine. The organic layer was dried over anhydrous Na2SO4, and concentrated at low pressure. The residue was purified on silica gel column (PE/EA=2/1) to give pure 30-2 (45 g, 73%) as a white solid

Reference： [1]Patent: US2015/105341,2015,A1 .Location in patent: Paragraph 0481

61
[ 14215-97-5 ]
[ 115459-50-2 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen bromide; In acetic acid; at 20℃; for 3h;	2.9 mL of 30% hydrogen bromide/acetic acid was added dropwise to a suspension of 5.0 g of <strong>[14215-97-5]1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose</strong> in 1.3 mL of acetic acid at room temperature, and the obtained mixture was then stirred at room temperature for 3 hours. Thereafter, 20 mL of toluene and 20 mL of water were added to the reaction mixture, and the obtained mixture was then stirred for 5 minutes. Thereafter, the water layer was removed. The obtained organic layer was washed with 20 mL of a 10% sodium hydrogen carbonate aqueous solution, and the solvent was then distilled away under reduced pressure. 10 mL of acetonitrile and 10 mL of a 10% sodium hydrogen carbonate aqueous solution were added to the obtained oily product, and the obtained mixture was then stirred at room temperature for 1 hour and was then left overnight. Thereafter, 20 mL of toluene and 10 mL of water were added to the reaction mixture, and the obtained mixture was then stirred for 5 minutes. After that, the water layer was removed, and the solvent was then distilled away under reduced pressure, so as to obtain a colorless oily product containing 2,3,5-tri-O-benzoyl-D-ribofuranose. [1601] The colorless oily product was directly used in the subsequent reaction

Reference： [1]Patent: US2015/152131,2015,A1 .Location in patent: Paragraph 1600-1601

62
[ 14215-97-5 ]
pre-silylated 6-chloroguanine [ No CAS ]
[ 3387-63-1 ]

Yield	Reaction Conditions	Operation in experiment
73%	With trimethylsilyl trifluoromethanesulfonate; In 1,2-dichloro-ethane; at 0 - 70℃; for 16h;	To a mixture of pre-silylated 6-Cl-guanine (using HMDS and (NH4)2SO4) (25.2 g, 150 mmol) in DCE (300 mL) was added 30-1 (50 g, 100 mmol) and TMSOTf (33.3 g, 150 mmol) at 0 C. The mixture was stirred at 70 C. for 16 h, and then concentrated at low pressure. The residue was re-dissolved in EA, and washed with sat. aq. NaHCO3 and brine. The organic layer was dried over anhydrous Na2SO4, and concentrated at low pressure. The residue was purified on silica gel column (PE/EA=2/1) to give pure 30-2 (45 g, 73%) as a white solid.

Reference： [1]Patent: US2015/366887,2015,A1 .Location in patent: Paragraph 0349-0350

63
[ 4212-49-1 ]
[ 14215-97-5 ]
[ 25692-02-8 ]

Yield	Reaction Conditions	Operation in experiment
95%		Compound 105: To a solution of compound 104 (2.8 g, 20 mmol) in dry acetonitrile (30 mL) was added BSA (21 g, 100 mmol, 5 eq). The reaction mixture was stirred at 60 C for 4 h and cooled to room temperature. To this reaction mixture were added compound 103 (10.1 g, 20 mmol), TMSOTf (10.8 mL, 60 mmol, 3eq), and the resulted reaction mixture was stirred at 60 C for 4 h. Uponcompletion of the reaction as monitored by TLC, the reaction mixture was treated with methylene chloride and saturated sodium bicarbonate. The organic phase was separated, and the aqueous phase was extracted with dichloromethane. The combined organic phase was dried over anhydrous Na2SO4. The drying agent was filtered off, and the filtrate was concentrated under reduced pressure. The crude product was purified by flash chromatography on a silica gel column giving 11 g desiredcompound 105 in 95% yield.
95%		Compound 1 05: To a solution of compound 1 04 (2.8 g, 20 mmol) in dry acetonitrile (30 mL) s added BSA (21 g, 100 mmol, 5 eq). The reaction mixture was stirred at 60 C for 4 h and cooled oom temperature. To this reaction mixture were added compound 103 (1 0.1 g, 20 mmol), TMSOTf .8 mL, 60 mmol, 3eq), and the resulted reaction mixture was stirred at 60 C for 4 h. Upon mpletion of the reaction as monitored by TLC, the reaction mixture was treated with methylene oride and saturated sodium bicarbonate. The organic phase was separated, and the aqueous ase was extracted with dichloromethane. The combined organic phase was dried over anhydrous 2S04. The drying agent was filtered off, and the filtrate was concentrated under reduced pressure. e crude product was purified by flash chromatography on a silica gel column giving 1 1 g desired mpound 105 in 95% yield.

Reference： [1]Patent: WO2015/196130,2015,A2 .Location in patent: Page/Page column 609
[2]Patent: WO2015/196128,2015,A2 .Location in patent: Page/Page column 617

64
[ 14215-97-5 ]
[ 6623-81-0 ]
[ 37805-86-0 ]

Yield	Reaction Conditions	Operation in experiment
65%		Compound 110: To a solution of compound 109 (1 .42 g, 10 mmol) in dry acetonitrile (30 mL) was added BSA (10.5 g, 50 mmol). The reaction mixture was stirred at 60 C for 4 h and cooled to room temperature. To the reaction mixture were added compound 103 (5.04 g, 1 0 mmol) andTMSOTf (2.7 mL, 15 mmol). The resulted reaction mixture was stirred at 60 CC for 4 h. Upon completion of the reaction as monitored by TLC, the reaction mixture was treated with methylene chloride and saturated sodium bicarbonate. The organic phase was separated, and the aqueous phase was extracted with methylene chloride. The combined organic phase was dried over anhydrous Na2504. The drying agent was filtered off, and the filtrate was concentrated under reduced pressure. The crude product was purified by flash chromatography on a silica gel column giving 3.8 g desired compound 110 in 65% yield.
65%		Compound 1 1 0: To a solution of compound 1 09 (1 .42 g, 1 0 mmol) in dry acetonitrile (30 mL) s added BSA (1 0.5 g, 50 mmol). The reaction mixture was stirred at 60 C for 4 h and cooled to m temperature. To the reaction mixture were added compound 1 03 (5.04 g, 1 0 mmol) and SOTf (2.7 mL, 15 mmol). The resulted reaction mixture was stirred at 60 C for 4 h. Upon mpletion of the reaction as monitored by TLC, the reaction mixture was treated with methylene oride and saturated sodium bicarbonate The organic phase was separated and the aqueous ase was anhydrous N ressure. The crude product was purified by flash chromatography on a silica gel column giving 3.8 g sired compound 1 1 0 in 65% yield.

Reference： [1]Patent: WO2015/196130,2015,A2 .Location in patent: Page/Page column 610; 611
[2]Patent: WO2015/196128,2015,A2 .Location in patent: Page/Page column 618; 619

65
[ 141-90-2 ]
[ 14215-97-5 ]
[ 21052-18-6 ]

Yield	Reaction Conditions	Operation in experiment
89%		Synthesis of Compound 139. To a solution of compound 114 (24.0 g, 187.2 mmol) inhexamethyldisilazane (960 mL) were added trimethyl chlorosilane (21 .60 mL, 169.70 mmol) and thecatalytic amount of ammonium sulfate (1 .0 g, 75 mmol). The clear reaction mixture was stirred at 126cc for 1 8 h. The reaction mixture became clear, and concentrated under reduced pressure to drynessat not more than 45 C. A solution of 1 ,2,3,5-tetra-O-acetyl-D-robofuranose (66 g, 207.60 mmol) indry 1 ,2-dichloroethane (240 mL) was added to the reaction mixture, followed by addition of tintetrachloride (28.80 mL, 249.6 mmol). The reaction mixture was stirred at room temperature for 1 h. Upon completion of the reaction as monitored by TLC, the reaction mixture was poured into saturated sodium bicarbonate (1000 mL) and stirred for 1 h. The solid was filtered off through a pad of Celite, and washed with methylene chloride. The organic phase separated, and the aqueous phase was extracted with dichioromethane. The combined organic phase was dried over anhydrous Na2SO4.The drying agent was filtered off, and the filtrate was concentrated under reduced pressure. Thecrude product was purified by flash chromatography on a silica gel column using ethyl acetate -petroleum ether (1:2 to 1:1) resulting in compound 139 (65.0 g, 1 68.2 mmol) in 89 % yield.

Reference： [1]Patent: WO2015/196130,2015,A2 .Location in patent: Page/Page column 619; 620

66
[ 14215-97-5 ]
<7-¹⁵N>-hypoxanthine [ No CAS ]
[¹⁵N⁽⁷⁾]-2',3',5'-tri-O-benzoylinosine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%		15N(7)-Hypoxanthine 5 (2.00 g, 14.6 mmol) and 7.36 g1-O-acetyl-2,3,5-O-tribenzoylribofuranose (14.6 mmol)were suspended in 100 cm3 of dry toluene. N,OBis(trimethylsilyl)acetamide (10.7 cm3, 43.8 mmol) wasadded and the suspension refluxed for 30 min upon which aclear yellow solution formed. At this point 7.9 cm3trimethylsilyl triflate (43.8 mmol) was added and refluxingwas continued for 45 min. All volatiles were evaporatedand the residue was dissolved in 350 cm3 of dichloromethaneand 150 cm3 of saturated sodium bicarbonatesolution. The organic layer was washed with 150 cm3 ofbrine, dried over Na2SO4, filtered, and evaporated. Thecrude product was purified by silica gel column chromatography,eluting with 0-5% methanol indichloromethane. Compound 6 was obtained as an offwhitefoam. Yield: 4.72 g (56%); Rf = 0.20 (MeOH/CH2Cl2 5:95); 1H NMR (300 MHz, DMSO-d6):d = 4.64-4.88 (m, 3H, H-C(40), 2 9 H-C(50)), 6.19 (t,J = 5.9 Hz, 1H, H-C(30)), 6.40 (t, J = 5.3 Hz, 1H,H-C(20)), 6.57 (d, J = 4.6 Hz, 1H, H-C(10)), 7.41-7.53(m, 6H, H-C(ar, Bz)), 7.61-7.69 (m, 3H, H-C(ar, Bz)),7.88-8.00 (m, 7H, H-C(2), H-C(ar, Bz)), 8.38 (d, J1H15-N = 12.0 Hz, 1H, H-C(8)), 12.49 (br s, 1H, H-N(1)) ppm;13C NMR (75 MHz, DMSO-d6): d = 63.25 (C(50)), 70.69 (C(30)), 73.31 (C(20)), 79.31 (C(40)), 86.51 (C(10)), 125.04(C(ar)), 128.30 (C(ar, Bz)), 128.75 (C(ar, Bz)), 129.29(C(ar, Bz)), 129.37 (C(ar, Bz)), 133.52 (C(ar, Bz)), 133.89(C(ar, Bz)), 134.00 (C(ar, Bz)), 139.78 (C(8)), 146.15(C(2)), 147.89 (C(ar)), 156.39 (C(ar)), 164.50 (CO(Bz)),164.68 (CO(Bz)), 165.42 (CO(Bz)) ppm; ESI-MS: m/z = 581.88 ([M ? H]

Reference： [1]Monatshefte fur Chemie,2017,vol. 148,p. 149 - 155

67
[ 679834-45-8 ]
[ 14215-97-5 ]
[ 679834-46-9 ]

Yield	Reaction Conditions	Operation in experiment
		To a 100-L jacketed reactor were charged 4-amino-6- bromo-2-methyl-7H-pyrrolo[2, 3 -d]pyrimidine-5 -carbonitrile (3.00 kg), (3R,4R, 5R)-2-acetoxy-5 - ((benzoyloxy)methyl)tetrahydrofuran-3,4-diyl dibenzoate (6.60 kg) and DCE (18.89 kg). Stirring was started and DBU (3.61) kg was added. Over a period of 03 h and 14 mi TMSOTf (8.01 kg) was added between 30.6 C and 37.3 C. IPC after 01 h and 30 mm at approx. 32 C showed 4% of 4-amino-6-bromo-2-methyl-7H-pyrrolo[2, 3 -d]pyrimidine-5 -carbonitrile (3.00 kg), (3R,4R, 5R)-2-acetoxy-5 -((benzoyloxy)methyl)tetrahydrofuran-3 ,4-diyl dibenzoate remaining. IPC after 03h and 16 mm at approx. 32 C showed 2% 4-amino-6-bromo-2-methyl-7H- pyrrolo[2,3 -d]pyrimidine-5-carbonitrile (3.00 kg), (3R,4R, 5R)-2-acetoxy-5- ((benzoyloxy)methyl)tetrahydrofuran-3 ,4-diyl dibenzoate remaining (spec: 3 %). The reaction mixture was diluted with DCM (39.81 kg) and quenched with potable water (15.02 kg) over an 11 mm period between 9.5 C and 15.6 C. The extractive work-up (at approx. 22 C) was completed by a back extraction of the aqueous phase with DCM (19.90 kg), a wash with sat NaHCO3 (1.3 kg NaHCO3 in 14.9 kg potable water), a back extraction of the bicarbonate phase with DCM (19.71 kg) and a wash with brine (4.5 kg NaC1 in 14.9 kg potable water). Note: the reactor was cleaned with potable water, acetone and DCM after each wash/back extraction.

Reference： [1]Patent: WO2017/24310,2017,A1 .Location in patent: Paragraph 00315-00318

68
[ 2164-84-3 ]
[ 14215-97-5 ]
[ 112220-31-2 ]