Name: 148579-94-6|(2S,3R,4S,5S,6S)-2-(4-(Hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate|97%
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1
[ 7693-46-1 ]
[ 148579-94-6 ]
[ 148580-01-2 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine In dichloromethane; acetonitrile at 0℃; for 1.5h;

Reference： [1]Florent, Jean-Claude; Dong, Xia; Gaudel, Gilbert; Mitaku, Sofia; Monneret, Claude; Gesson, Jean-Pierre; Jacquesy, Jean-Claude; Mondon, Martine; Renoux, Brigitte; Andrianomenjanahary, Solo; Michel, Sylvie; Koch, Michel; Tillequin, François; Gerken, Manfred; Czech, Joerg; Straub, Rainer; Bosslet, Klaus [Journal of Medicinal Chemistry, 1998, vol. 41, # 19, p. 3572 - 3581]

2
[ 148579-93-5 ]
[ 148579-94-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium tetrahydridoborate In chloroform; isopropanol at 0 - 20℃;
99%	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol at 0℃; for 0.75h;
96%	With sodium tetrahydridoborate; mesoporous silica; isopropanol In chloroform at 0℃; for 0.75h;

95%	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol at 0℃; for 0.75h; Inert atmosphere;
92%	With sodium tetrahydridoborate; mesoporous silica In chloroform; Isopropyl acetate for 0.75h;	1; 2 Methyl 1-(4-hydroxymethyl-2-nitrophenyl)-2,3,4-tri-O-acetyl-β-D-glucopyronuronate (7) (See, e.g., Florent et al., J. Med. Chem. 1998, 41, 3572-3581; Leu et al., J. Med. Chem. 1999, 42, 3623-3628): 1.41 g (37.3 mmol) NaBH4 were added to a stirring solution of 12.03 g (24.9 mmol) 6 and 5 g silica gel at 0° C. in 300 ml 1:5 IPA:CHCl3. After 45 min, the solution was poured into 300 ml ice water and filtered through Celite. The layers were separated and the organic fraction washed with brine, dried (MgSO4), concentrated in vacuo, and triturated with Et2O, yielding 7 as a white solid (11.65 g, 96%).Coupling of 4-hydroxy-3-nitrobenzaldehyde to the pyranose via a Koenigs-Knorr reaction followed by sodium borohydride reduction produced 7 in 92% yield without recourse to chromatography.
92.4%	With sodium tetrahydridoborate; mesoporous silica; isopropanol In chloroform at 20℃; for 1h;	2.2 Step 2: Compound 2 To a stirred solution of compound 1 (9.00 g; 18.62 mmol; 1.00 eq.) in Propan-2-ol (33.00 ml; 3.67 V) and CHC (167.00 ml; 18.56 V) were added silica gel 60-120 (3.60 g; 112.09 mmol; 6.02 eq.) followed by sodium borohydride (1.80 g; 46.55 mmol; 2.50 eq.). The reaction mixture was stirred for 1 h at RT. After completion, the reaction mixture was quenched with cooled H2O and filtered through celite. The filtrate was extracted with Dichloromethane and dried over Na2SC>4. The solvent was concentrated to get compound 2 as off-white powder. Yield: 8.70 g Percentage Yield: 92.4% Analytical data LCMS: Column: ATLANTIS dC18 (50x4.6mm) 5 pm; Mobile phase A: 0.1 % HCOOH in H2O: ACN (95:5); B: ACN RT (min): 2.05; M+H: 503.2, Purity: 96.6%
92.4%	With sodium tetrahydridoborate; mesoporous silica; isopropanol In chloroform at 20℃; for 1h;	2.2 Step 2: Compound 2 To a stirred solution of compound 1 (9.00 g; 18.62 mmol; 1.00 eq.) in Propan-2-ol (33.00 ml; 3.67 V) and CHC (167.00 ml; 18.56 V) were added silica gel 60-120 (3.60 g; 112.09 mmol; 6.02 eq.) followed by sodium borohydride (1.80 g; 46.55 mmol; 2.50 eq.). The reaction mixture was stirred for 1 h at RT. After completion, the reaction mixture was quenched with cooled H2O and filtered through celite. The filtrate was extracted with Dichloromethane and dried over Na2SC>4. The solvent was concentrated to get compound 2 as off-white powder. Yield: 8.70 g Percentage Yield: 92.4% Analytical data LCMS: Column: ATLANTIS dC18 (50x4.6mm) 5 pm; Mobile phase A: 0.1 % HCOOH in H2O: ACN (95:5); B: ACN RT (min): 2.05; M+H: 503.2, Purity: 96.6%
91%	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol at 0℃; Inert atmosphere;
91%	With sodium tetrahydridoborate In methanol at 20℃; for 2h; Inert atmosphere;	3 Step 3. Synthesis of Compound 29 To a stirred solution of methyl (2S,3S,4S,5R,6S)-3,4,5-tris(acetyloxy)-6-(4-formyl-2-nitrophenoxy)oxane-2-carboxylate (Compound 28, 6.00 g, 12.41 mmol, 1.00 equiv) in MeOH (50 mL) were added NaBH4 (0.47 g, 12.42 mmol, 1.00 equiv) in portions at RT under N2 atmosphere. The resulting mixture was stirred for 2 h at room temperature under N2 atmosphere. LCMS indicated the reaction was completed. The reaction was quenched with water at room temperature. The resulting was dried by Na2SO4.The resulting mixture was filtered, the filter cake was washed with DCM. The resulting mixture was concentrated under vacuum to afford methyl (2S,3S,4S,5R,6S)-3,4,5-tris(acetyloxy)-6-[4-(hydroxymethyl)-2-nitrophenoxy]oxane-2-carboxylate (Compound 29, 5.5 g, 91%) as a solid. LCMS (ES, m/z):486 [M+H]+.
90%	With sodium tetrahydridoborate In dichloromethane at 0℃; for 1.16667h;	5 Synthesis of (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-mtrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate 21: The aryl aldehyde (1.5 g, 3 10 mmol) above was dissolved in CH2CI2 (15 mL) and IP A (3.5 mL). The resulting mixture was cooled to 0 °C and solid NaBK (71 mg, 1.87 mmol) was added in three portions over 10 minutes. After the addition, temperature was maintained at 0 °C for 1 hour. The reaction was poured into ice water (40 mL) which was followed by CH2CI2 (200 mL). The reaction mixture was stirred for 30 minutes and the layers were separated. The aqueous layer was back extracted with CH2CI2 and the combined organic layers were dried over MgSOi, filtered and evaporated to give an oily solid. Toluene was added to the mixture and evaporated to dryness two more times to give 1.35 g of a white solid for a 90% yield. MS (ESI): m/e 485.4, (M + Na)+, 508.
89%	Stage #1: (2S,3R,4S,5S,6S)-2-(4-formyl-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol at 0℃; for 1h; Stage #2: With hydrogenchloride; lithium hydroxide monohydrate In chloroform-d1; isopropanol	Methyl l-0-[2-iiitro-4-(/iydroxymet/iyl) phenyl]-2,S,4-tri-0-ucetyl-ft-B- glucopyvcmuronate, compound 12, scheme I.[0047] A mixture of 11 (0.9 g, 1.86 mmol), NaBH4 (0.14 g, 3.72 mmol) and silica gel (2 g) in ;-PrOH/CHCl3 (1:5) (60 ml) was stirred at 0°C for 1 h. The reaction was quenched with IN HC1 and filtered to remove silica gel. The organic layer was washed by water, then dried over anhydrous Na2S04 and evaporated under reduced pressure to give a residue which was crystallized with EtOH to give 12 (0.8 g, 89%) mp 167- 168°C, ' H NMR (200 MHz, DMSO-t/6) δ 1.98 (d, J= 4.0 Hz, 9 H) 3.63 (s, 3 H), 4.49 (s, 2 H), 4.71 (d, J= 9.8 Hz, 1 H), 5.07 (t, J= 9.5 Hz, 2 H), 5.44 (t, J= 9.4 Hz, 2 H), 5.69 (d, J= 7.74 Hz, 1 H), 7.37 (d, J= 8.6 Hz, 1 H), 7.59 (d, J = 8.6 Hz, 1 H), 7.78 (s, 1 H); l 3C NMR (50 MHz, DMSO-t/6) <5 21 .0, 21 .1 , 21 .2, 53.5, 62.2, 69.6, 70.8, 71 .7, 71 .9, 98.9, 1 18.6, 123.2, 132.9, 139.4, 141 . 1 , 147.8, 167.8, 169.6, 170.2, 170.4; FABMS m/z 426 (M+ - OCOCH3).
88%	With sodium tetrahydridoborate In tetrahydrofuran at 0℃; for 0.5h;	4.3. (2S,3R,4S,5S,6S)-2-(4-(Hydroxymethyl)phenoxy)-6-(methoxycarbonyl)-2H-tetrahydropyran-3,4,5-triyl triacetate (6a) General procedure: To a round-bottom flask was added compound 5a (590 mg,1.35 mmol), NaBH4 (56 mg, 1.48 mmol) and dry THF (10 mL), thereaction mixture was stirred at 0 C for 30 min. The mixture wasdiluted with a saturated aqueous solution of ammonium chloride(75 mL), and extracted with CH2Cl2 (3 25 mL) and EtOAc(3 25 mL). The organic layer were combined, dried over anhydrousNa2SO4, concentrated and purified by silica column chromatography(EtOAc/PE 1:1, v/v) to afford product 6a as whitesolid (450 mg, yield 85%);
88%	With sodium tetrahydridoborate In tetrahydrofuran at 0℃; for 0.5h;	4.3. (2S,3R,4S,5S,6S)-2-(4-(Hydroxymethyl)phenoxy)-6-(methoxycarbonyl)-2H-tetrahydropyran-3,4,5-triyl triacetate (6a) General procedure: To a round-bottom flask was added compound 5a (590 mg,1.35 mmol), NaBH4 (56 mg, 1.48 mmol) and dry THF (10 mL), thereaction mixture was stirred at 0 C for 30 min. The mixture wasdiluted with a saturated aqueous solution of ammonium chloride(75 mL), and extracted with CH2Cl2 (3 25 mL) and EtOAc(3 25 mL). The organic layer were combined, dried over anhydrousNa2SO4, concentrated and purified by silica column chromatography(EtOAc/PE 1:1, v/v) to afford product 6a as whitesolid (450 mg, yield 85%);
84%	With sodium tetrahydridoborate; isopropanol In chloroform at 0℃; for 1h;	1.2 Intermediate 2.45: 1-(hydroxymethyl-2-nitrophenoxy)-(Methyl-2,3,4-tri-0-acetyl)-D- glucopyranouronate Intermediate 2.44 (5.22 g, 10.1 mmol) was reduced with sodium borohydride (4.90 g, 130.0 mmol) in 65 mL of 1:5 2-propanol/CHCI3 (volume ratio). The mixture was stirred under for lh at 0°C. The reaction was filtered over Celite, the filtrate was concentrated in vacuo to afford 4.40 g (84%, yield) of Intermediate 2.45. XH NMR (DMSO d6, 400 MHz) d 7.99 (s, 1H), 7.62 (d, 1H), 7.38 (d, 1H), 5.72 (m, 1H), 5.45 (m, 1H), 5.09 (q, 2H), 4.73 (d, 1H), 4.51 (s, 2H), 3.65 (s, 3H), and 2.02 (m, 9H). LC-MS: Rt = 3.33 min, m/z = 486 [M+H]+, m/z = 484 [M-H]-
82%	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol at 0 - 20℃;
78%	With sodium tetrahydridoborate In chloroform; isopropanol at 0 - 5℃; for 3h;
77%	With sodium tetrahydridoborate; mesoporous silica; triethylamine; isopropanol In chloroform at 0℃; for 2h;	2.2-2 Step 2-2-Preparation of (2S,3R,4S,5S,6S)-2-(4-(Hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl Triacetate Step 2-2-Preparation of (2S,3R,4S,5S,6S)-2-(4-(Hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl Triacetate To an ice cold solution of (2S,3R,4S,5S,6S)-2-(4-formyl-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (52.0 g, 107.7 mmol) and silica gel (80 g) in IPA/chloroform (1 L, 3:7) was added sodium borohydride (11.0 g, 290.7 mmol); followed by addition of triethylamine (1.60 mL, 11.77 mmol). The reaction mixture was stirred at 0° C. for 2 h (reaction complete by TLC monitoring). The reaction mixture was then quenched with ice water and the resulting mixture was filtered. The filtrate was concentrated under reduced pressure and the crude residue was crystallized using ethanol. The resulting solid was isolated by filtration and then dried under reduced pressure to afford the title compound (40.0 g, 77%) as off white solid.
76%	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol at 0℃; for 1h;
72%	With sodium tetrahydridoborate In methanol; dichloromethane at 0℃; for 0.5h;	7 (2S,3S,4S,5R,6R)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(2-methoxy-2-oxoethyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (2S,3S,4S,5R,6R)-2-(4-formyl-2-nitrophenoxy)-6-(2-methoxy-2-oxoethyl)tetrahydro-2H- pyran-3,4,5-triyl triacetate (500mg, 1.03 mmol) was dissolved in dichloromethane (20 mL) and methanol (20 mL) and cooled to 0°C on ice-bath. Sodium borohydride (65 mg, 1.50 mmol) was added and stirred. After 30 min TLC indicated complete conversion and saturated solution of ammonium sulphate (40 mL) was added to quench the reaction. The product was extracted with dichloromethane (3x30 mL), the organic phase dried with sodium sulphate. After solvent evaporation colourless solid was obtained which was purified by Flash chromatography using dichloromethane/methanol gradient yielding colourless product (360 mg, 74.2 mmol, 72.0%). XH NMR (300 MHz, Acetonitrile-d3) δ 7.77 (d, J = 2.0 Hz, 1H), 7.56 (dd, J = 8.6, 2.1 Hz, 1H), 7.40 (d, J = 8.6 Hz, 1H), 5.51 - 5.35 (m, 2H), 5.33 - 5.16 (m, 2H), 4.59 (s, 2H), 4.42 (d, J = 9.7 Hz, 1H), 3.69 (s, 3H), 2.05 (s, 3H), 2.04 (s, 3H), 2.02 (s, 3H). 13C NMR (75 MHz, CD3CN) δ 170.03, 169.89, 169.44, 167.30, 147.88, 140.97, 138.49, 132.19, 122.89, 118.46, 117.62, 99.29, 72.10, 71.14, 70.33, 69.04, 62.29, 52.75, 20.11, 20.07, 20.03. LRMS, ESI: m/z 502.7 [M+NH4]+.
72%	With methanol; sodium tetrahydridoborate In dichloromethane at 0℃; for 0.5h; Inert atmosphere;	2 4.2.3 Methyl 1-(4-hydroxymethyl-2-nitrophenyl)-2,3,4-triacetyl-β-d-glucopyranuronate (3) Compound 2 (232mg, 0.48mmol) was dissolved in DCM (10mL) and MeOH (10mL) and cooled to 0°C. NaBH4 (30mg, 0.72mmol) was added slowly to the reaction mixture. After 30min NH4Cl (20mL) was added and extracted with DCM (3×15 mL). The organic phase was dried with Na2SO4 and evaporated to dryness. The crude product was purified by Flash chromatography using DCM/MeOH gradient yielding colorless solid (168mg, 0.35mmol, 72.0%). (168mg, 0.35mmol, 72.0%). 1H NMR (500MHz, CD3CN) δ 7.76 (d, J=2.1Hz, 1H), 7.54 (dt, J=8.7, 2.1, 1.9Hz, 1H), 7.38 (d, J=8.6Hz, 1H), 5.49-5.33 (m, 2H), 5.31-5.14 (m, 2H), 4.58 (s, 2H), 4.41 (d, J=9.8Hz, 2H), 3.67 (s, 3H), 2.02 (s, 3H), 2.01 (s, 3H), 1.99 (s, 3H). 13C NMR (126MHz, Acetonitrile-d3) δ 170.03, 169.89, 169.44, 167.30, 147.88, 138.52, 132.19, 122.90, 118.49, 117.61, 99.32, 72.13, 71.18, 70.36, 69.06, 62.31, 52.75, 20.11, 20.07, 20.03.
66%	With sodium tetrahydridoborate; isopropanol In dichloromethane at 0 - 5℃;	1.b (b) (25,3R,45,55,65)-2-(4-(hydroxymethyl)-2-nitro- phenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (10) (b) (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (10) To a 1 L 3-neck flask equipped with a mechanical stirrer was added Compound 9 (32.7 g, 67.6 mmol) followed by DCM (350 mL) and IPA (70 mL). The reaction mixture was stirred to dissolve the solid and then cooled to 0° C. To the solution was added sodium borohydride (1.54 g, 40.6 mmol) in three portions, keeping the temperature below 5° C., and the reaction mixture was stirred at 0° C. for 1 h and slowly poured into ice water (400 mL). To the solution was added DCM (350 mL) and the mixture was stirred for 30 min, allowed to settle for 30 min and the layers were separated. The aqueous layer was back extracted with DCM (100 mL). The combined organic layers were washed with brine (500 mL). After 30 min, the layers were separated and the brine layer was back extracted with DCM (100 mL). The combined organic layers were dried over sodium sulfate (50 g) for 2 h, filtered through Celite, and distilled under reduced pressure to dryness. The resulting solid was stirred with 95% denatured EtOH (130 mL) at 50° C. for 30 min and at RT for 12 h to form a crystalline solid which was washed with EtOH (30 mL) and dried under vacuum at RT for 16 h to provide the title compound as a white solid (21 g, 66% yield 98% purity) HPLC Method A Retention time 13.18 min.
62%	With sodium tetrahydridoborate; isopropanol In chloroform at 0℃; for 2.5h; Inert atmosphere;
32%	Stage #1: (2S,3R,4S,5S,6S)-2-(4-formyl-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate With mesoporous silica In dichloromethane; isopropanol at 0℃; for 0.5h; Stage #2: With sodium tetrahydridoborate In dichloromethane; isopropanol at 0℃; for 1h;
	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol Inert atmosphere;
	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol at 0℃; for 0.75h;	2.35.2 2.35.2. (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2- nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5- triyl triacetate To a solution of Example 2.35.1 (6 g) in a mixture of chloroform (75 mL) and isopropanol (18.75 mL) was added 0.87 g of silica gel. The resulting mixture was cooled to 0 °C, NaBH4 (0.470 g) was added, and the resulting suspension was stirred at 0 °C for 45 minutes. The reaction mixture was diluted with dichloromethane (100 mL) and filtered through diatomaceous earth. The filtrate was washed with water and brine and concentrated to give the crude product, which was used without further purification. MS (ESI) m/e (M+NH4)+:
	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol at 0℃; for 0.75h;	2.2.55.2.55.2 2.55.2. (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate [000953] To a solution of Example 2.55.1 (6 g) in a mixture of chloroform (75 mL) and isopropanol (18.75 mL) was added 0.87 g of silica gel. The resulting mixture was cooled to 0 °C, NaBH4 (0.470 g) was added, and the resulting suspension was stirred at 0 °C for 45 minutes. The reaction mixture was diluted with dichloromethane (100 mL) and filtered through diatomaceous earth. The filtrate was washed with water and brine and concentrated to give the crude product, which was used without further purification. MS (ESI) m/e (M+NH4)+:
	With sodium tetrahydridoborate; mesoporous silica; isopropanol In chloroform at 0℃; for 0.75h;	2.2.32.2.32.2 2.32.2 (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate To a solution of Example 2.32.1 (6 g) in a mixture of chloroform (75 mL) and isopropanol (18.75 mL) was added 0.87 g of silica gel. The resulting mixture was cooled to 0 °C, NaBH4 (0.470 g) was added, and the resulting suspension was stirred at 0 °C for 45 minutes. The reaction mixture was diluted with dichloromethane (100 mL) and filtered through diatomaceous earth. The filtrate was washed with water and brine and concentrated to give the crude product, which was used without further purification. MS (ESI) m/e (M+NH4)+:
	With sodium tetrahydridoborate; mesoporous silica; isopropanol In chloroform at 0℃; for 0.75h;	2.2.55.2.55.2 2.55.2 (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6- (methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate To a solution of Example 2.55.1 (6 g) in a mixture of chloroform (75 mL) and isopropanol (18.75 mL) was added 0.87 g of silica gel. The resulting mixture was cooled to 0 °C, NaBH4 (0.470 g) was added, and the resulting suspension was stirred at 0 °C for 45 minutes. The reaction mixture was diluted with dichloromethane (100 mL) and filtered through diatomaceous earth. The filtrate was washed with water and brine and concentrated to give the crude product, which was used without further purification. MS (ESI) m/e (M+NH4)+:
	With sodium tetrahydridoborate In chloroform; isopropanol at 0℃; for 0.75h;	2.55.2 2.55.2 (25,3R,45,55,65)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate To a solution of Example 2.55.1 (6 g) in a mixture of chloroform (75 mL) and isopropanol (18.75 mL) was added 0.87 g of silica gel. The resulting mixture was cooled to 0° C.NaBH4 (0.470 g) was added, and the resulting suspension was stirred at 00 C. for 45 minutes. The reaction mixture was diluted with dichloromethane (100 mL) and filtered through diatomaceous earth. The filtrate was washed with water and brine and concentrated to give the crude product, which was used without thrther purification. MS (ESI) m/e (M+NH4)+:
	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol
	With sodium tetrahydridoborate In dichloromethane; isopropanol at 0 - 5℃; for 1h;	1.b (b) (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (10) To a 1 L 3-neck flask equipped with a mechanical stirrer was added Compound 19 9 (32.7 g, 67.6 mmol) followed by 21 DCM (350 mL) and IPA (70 mL). The reaction mixture was stirred to dissolve the solid and then cooled to 0° C. To the solution was added 22 sodium borohydride (1.54 g, 40.6 mmol) in three portions, keeping the temperature below 5° C., and the reaction mixture was stirred at 0° C. for 1 h and slowly poured into ice water (400 mL). To the solution was added DCM (350 mL) and the mixture was stirred for 30 min, allowed to settle for 30 min and the layers were separated. The aqueous layer was back extracted with DCM (100 mL). The combined organic layers were washed with brine (500 mL). After 30 min, the layers were separated and the brine layer was back extracted with DCM (100 mL). The combined organic layers were dried over sodium sulfate (50 g) for 2 h, filtered through Celite, and distilled under reduced pressure to dryness. The resulting solid was stirred with 95% denatured 23 EtOH (130 mL) at 50° C. for 30 min and at RT for 12 h to form a crystalline solid which was washed with EtOH (30 mL) and dried under vacuum at RT for 16 h to provide the 24 title compound as a white solid (21 g, 66% yield 98% purity) HPLC Method A Retention time 13.18 min.
	With sodium tetrahydridoborate; mesoporous silica In chloroform; isopropanol at 0℃; for 0.75h;	2.35.2 2.35.2. (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate To a solution of Example 2.35.1 (6 g) in a mixture of chloroform (75 mL) and isopropanol (18.75 mL) was added 0.87 g of silica gel. The resulting mixture was cooled to 0° C., NaBH4 (0.470 g) was added, and the resulting suspension was stirred at 0° C. for 45 minutes. The reaction mixture was diluted with dichloromethane (100 mL) and filtered through diatomaceous earth. The filtrate was washed with water and brine and concentrated to give the crude product, which was used without further purification. MS (ESI) m/e (M+NH4)+:
	With sodium tetrahydridoborate; mesoporous silica; isopropanol In dichloromethane at 0℃; for 2h;	Intermediate A-2: (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(carbomethoxy)tetrahydro-2H-pyridine Furan-3,4,5-triyltriacetate Intermediate A-1 (46.5 g, 96 mmol) and 19 g of silica gel were dissolved in 450 mL of dichloromethane and 90 mL of isopropanol. The reaction was cooled to 0°C and 5.5 g of sodium borohydride was added slowly. The reaction solution was stirred at 0°C for 2 hours. Complete conversion of starting material was monitored by LCMS. The reaction solution was filtered, saturated ammonium chloride solution (200 mL) was added to the filtrate, the layers were separated, the organic phase was washed twice with saturated brine (300 mL), dried over anhydrous sodium sulfate, and spin-dried to obtain a crude product with methyl Slurried tert-butyl ether gave the title compound (34. g, 72.9%) as a white solid.

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[2]Florent, Jean-Claude; Dong, Xia; Gaudel, Gilbert; Mitaku, Sofia; Monneret, Claude; Gesson, Jean-Pierre; Jacquesy, Jean-Claude; Mondon, Martine; Renoux, Brigitte; Andrianomenjanahary, Solo; Michel, Sylvie; Koch, Michel; Tillequin, François; Gerken, Manfred; Czech, Joerg; Straub, Rainer; Bosslet, Klaus [Journal of Medicinal Chemistry, 1998, vol. 41, # 19, p. 3572 - 3581]
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[5]Current Patent Assignee: NORTHWESTERN UNIVERSITY (ILLINOIS) - US2006/88475, 2006, A1 Location in patent: Page/Page column 7; 12; 2 fig. 2A
[6]Current Patent Assignee: MERCK KGAA - WO2022/48883, 2022, A1 Location in patent: Page/Page column 68; 69-70
[7]Current Patent Assignee: MERCK KGAA - WO2022/48883, 2022, A1 Location in patent: Page/Page column 68; 69-70
[8]Walther, Raoul; Jarlstad Olesen, Morten T.; Zelikin, Alexander N. [Organic and Biomolecular Chemistry, 2019, vol. 17, # 29, p. 6970 - 6974]
[9]Current Patent Assignee: ORUM THERAPEUTICS INC. - WO2021/198965, 2021, A1 Location in patent: Paragraph 0525; 0528; 0555
[10]Current Patent Assignee: IL 2RX - WO2020/14541, 2020, A2 Location in patent: Paragraph 0546; 0568; 0571
[11]Current Patent Assignee: ACADEMIA SINICA - WO2011/66418, 2011, A1 Location in patent: Page/Page column 24-25
[12]Ding, Kuiling; Liang, Yuru; Peng, Yingyuan; Shi, Zhixian; Wang, Yang [European Journal of Medicinal Chemistry, 2022, vol. 236]
[13]Ding, Kuiling; Liang, Yuru; Peng, Yingyuan; Shi, Zhixian; Wang, Yang [European Journal of Medicinal Chemistry, 2022, vol. 236]
[14]Current Patent Assignee: INVIVOGEN SAS - WO2019/129880, 2019, A1 Location in patent: Page/Page column 58; 71
[15]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]
[16]Location in patent: scheme or table Kamal, Ahmed; Tekumalla, Venkatesh; Raju; Naidu; Diwan, Prakash V.; Sistla, Ramakrishna [Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 13, p. 3769 - 3773]
[17]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2018/339990, 2018, A1 Location in patent: Paragraph 0260; 0262; 0263
[18]Leu, Yu-Ling; Chen, Chien-Shu; Wu, Yih-Jang; Chern, Ji-Wang [Journal of Medicinal Chemistry, 2008, vol. 51, # 6, p. 1740 - 1746]
[19]Current Patent Assignee: UNIVERSITY OF GENEVA - WO2016/185368, 2016, A1 Location in patent: Page/Page column 67
[20]Herceg; Adriouach; Janikowska; Allémann; Lange; Babič [Bioorganic Chemistry, 2018, vol. 78, p. 372 - 380]
[21]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2017/145044, 2017, A1 Location in patent: Paragraph 0183; 0185
[22]López Rivas, Paula; Müller, Christoph; Breunig, Christian; Hechler, Torsten; Pahl, Andreas; Arosio, Daniela; Belvisi, Laura; Pignataro, Luca; Dal Corso, Alberto; Gennari, Cesare [Organic and Biomolecular Chemistry, 2019, vol. 17, # 19, p. 4705 - 4710]
[23]Calatrava-Pérez, Elena; Elmes, Robert B. P.; Gunnlaugsson, Thorfinnur; Lynch, Dylan M.; Marchetti, Luke A.; McManus, Gavin J.; Scanlan, Eoin M.; Williams, D. Clive [Chemistry - A European Journal, 2022, vol. 28, # 3]
[24]Pettit, George R.; Arce, Pablo M.; Chapuis, Jean-Charles; Macdonald, Christian B. [Journal of Natural Products, 2015, vol. 78, # 3, p. 510 - 523]
[25]Current Patent Assignee: ABBVIE INC - WO2016/94505, 2016, A1 Location in patent: Paragraph 000569
[26]Current Patent Assignee: ABBVIE INC - WO2016/94509, 2016, A1 Location in patent: Paragraph 000953
[27]Current Patent Assignee: ABBVIE INC - WO2017/214458, 2017, A2 Location in patent: Page/Page column 438
[28]Current Patent Assignee: ABBVIE INC - WO2017/214462, 2017, A2 Location in patent: Page/Page column 566
[29]Current Patent Assignee: ABBVIE INC - US2017/355769, 2017, A1 Location in patent: Paragraph 1932
[30]Walther, Raoul; Nielsen, Signe Maria; Christiansen, Rikke; Meyer, Rikke L.; Zelikin, Alexander N. [Journal of Controlled Release, 2018, vol. 287, p. 94 - 102]
[31]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2018/339980, 2018, A1 Location in patent: Paragraph 0216
[32]Current Patent Assignee: ABBVIE INC - US2019/153107, 2019, A1 Location in patent: Paragraph 1048
[33]Current Patent Assignee: ENNOVABIO ZHEJIANG PHARMACEUTICAL; SHANGHAI ENNOVABIO PHARMACEUTICALS; ENNOVABIO ZHEJIANG PHARMACEUTICALS - CN113943312, 2022, A Location in patent: Paragraph 0150-0151; 0156-0159

3
[ 148579-94-6 ]
methyl [2-nitro-4-(chloromethyl)phenyl] 2,3,4-tri-O-acetyl-β-D-glucopyranosid}uronate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20%	With methanesulfonyl chloride In pyridine for 3h; Heating;

Reference： [1]Azoulay, Michel; Chalard, Frederic; Gesson, Jean-Pierre; Florent, Jean-Claude; Monneret, Claude [Carbohydrate Research, 2001, vol. 332, # 2, p. 151 - 156]

4
[ 74124-79-1 ]
[ 148579-94-6 ]
[ 148579-95-7 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine In acetonitrile at 20℃; for 2h;
	With triethylamine In N,N-dimethyl-formamide; acetonitrile at 20℃; for 1h; Inert atmosphere;	4 4.2.5 Hexyl 5-(((4-(Methyl-(2,3,4-triacetyl-β-d-glucopyranuronate-1-yl)-3-nitrobenzyl)oxy) carbonyl) amino)-4-oxopentanoate (5) Compound 4 (20mg, 41µmol) and TEA (11.4µL, 82µmol) were dissolved in AcN (3.0mL) and DMF (1.0mL). N,N′-disuccinimidyl carbonate (15.8mg, 62µmol) was added and the reaction mixture stirred at ambient temperature for 1h. The reaction mixture was cooled to 0°C and hexyl 5-amino-4-oxopentanoate hydrochloride (21mg, 83µmol) and TEA (11.4µL, 82µmol) were added. After 1h at 0°C the temperature was allowed to rise to ambient. After stirring for 2h 64 DCM (20mL) was added and the organic phase washed with diluted HCl (0.01M, 2×5mL). The organic phase was evaporated in vacuo and purified by Flash chromatography using hexane/ethyl acetate gradient yielding a yellow sticky solid (25mg, 34µmol, 82.9%). 1H NMR (600MHz, CDCl3) δ 7.82 (d, J=2.2Hz, 1H), 7.55 (dd, J=8.6, 2.1Hz, 1H), 7.38 (d, J=8.5Hz, 1H), 5.41-5.28 (m, 3H), 5.22 (d, J=6.7Hz, 1H), 5.12 (s, 2H), 4.23 (d, J=8.9Hz, 1H), 4.19-4.07 (m, 2H), 4.07 (d, J=6.9Hz, 2H), 3.76 (s, 3H), 2.74 (dd, J=7.8, 5.7Hz, 2H), 2.67 (dd, J=7.1, 4.9Hz, 2H), 2.14 (s, 3H), 2.08 (s, 3H), 2.06 (s, 3H), 1.62 (dq, J=13.7, 6.1, 5.4Hz, 2H), 1.32 (m, 6H), 0.90 (t, J=6.8Hz, 3H). 13C NMR (151MHz, CDCl3) δ 203.53, 172.42, 170.02, 169.30, 169.24, 166.67, 155.59, 148.74, 141.21, 133.32, 132.86, 124.63, 120.13, 99.78, 72.57, 71.07, 70.14, 68.71, 65.13, 65.06, 53.07, 50.62, 34.39, 31.39, 28.51, 27.86, 25.52, 22.52, 20.60, 20.55, 20.52, 13.99. LRMS (ESI): m/z calculated for [M+NH4]+ 744.4, found 744.8. HRMS (ESI): m/z calculated for C32H42N2O17 [M+NH4]+ 744.2822, found 744.2831.

Reference： [1]Rawale, Sharad; Hrihorczuk, Lew M.; Wei, Wei-Zen; Zemlicka, Jiri [Journal of Medicinal Chemistry, 2002, vol. 45, # 4, p. 937 - 943]
[2]Herceg; Adriouach; Janikowska; Allémann; Lange; Babič [Bioorganic Chemistry, 2018, vol. 78, p. 372 - 380]

5
[ 148579-94-6 ]
[ 1053628-49-1 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide In acetone at 0℃; for 0.0833333h;

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

6
[ 148579-94-6 ]
[ 637330-32-6 ]

Yield	Reaction Conditions	Operation in experiment
65%	With sodium methylate In methanol at -15 - 20℃;

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

7
[ 75-44-5 ]
[ 144640-75-5 ]
[ 148579-94-6 ]
[ 832739-11-4 ]

Yield	Reaction Conditions	Operation in experiment
54%	Stage #1: phosgene; 3',5'-di-O-acetyl-O⁶-benzyl-2'-deoxyguanosine With pyridine In dichloromethane; toluene for 20h; Stage #2: (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate In dichloromethane; toluene at 20℃; for 2h;

Reference： [1]Wei, Guangping; Loktionova, Natalia A.; Pegg, Anthony E.; Moschel, Robert C. [Journal of Medicinal Chemistry, 2005, vol. 48, # 1, p. 256 - 261]

8
[ 75-44-5 ]
[ 152833-02-8 ]
[ 148579-94-6 ]
[ 832739-10-3 ]

Yield	Reaction Conditions	Operation in experiment
42%	Stage #1: phosgene; (2-amino-6-(benzyloxy)-9H-purin-9-yl)methyl pivalate With pyridine In dichloromethane; toluene for 20h; Stage #2: (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate In dichloromethane; toluene at 20℃; for 2h;

Reference： [1]Wei, Guangping; Loktionova, Natalia A.; Pegg, Anthony E.; Moschel, Robert C. [Journal of Medicinal Chemistry, 2005, vol. 48, # 1, p. 256 - 261]

9
[ 530-62-1 ]
[ 148579-94-6 ]
[ 866611-65-6 ]

Yield	Reaction Conditions	Operation in experiment
94%	With dmap In dichloromethane
94%	With dmap In dichloromethane for 2.25h;	1 Methyl 1-(4-(2-bromo-ethylcarbamoyloxymethyl)-2-nitrophenyl)-2,3,4-tri-O-acetyl-β-D-glucopyronuronate (9): 3.75 g (7.73 mmol) sugar 7 and 189 mg (1.55 mmol) DMAP in 50 ml dry CH2Cl2 under N2 were subjected to 2.51 g (15.5 mmol) 1,1'-carbonyl-diimidazole. When the reaction was complete by TLC (silica, 5% MeOH/CH2Cl2) (2.25 h), the solution was washed with water, 5% NaH2PO4, sat. NaHCO3, and brine. The organic layer was dried (MgSO4) and concentrated in vacuo to yield 4.19 g of the imidazolyl intermediate 8.
	In dichloromethane at 20℃; for 3h;	2 Preparation 2: (25,35,45,5R,65)-2-(methoxycarbo- nyl)-6-(4-(((methyl(2-(methylamino)ethyl)carbam- oyl)oxy)methyl)-2-nitrophenoxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate (12) Preparation 2 (2S,3S,4S,5R,6S)-2-(methoxycarbonyl)-6-(4-(((methyl(2-(methylamino)ethyl)carbamoyl)oxy)methyl)-2-nitrophenoxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate (12) To a 100 mL flask equipped with a magnetic stirrer was added (2S,3R,4S,5S,6S)-2-(4-(hydroxymethyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyltriacetate (10) (4.86 g, 10 mmol) and carbonyldiimidazole (2.11 g, 13 mmol) followed by DCM (50 mL). The reaction mixture was stirred at RT for 3 h to form a solution of (2S,3R,4S,5S,6S)-2-(4-(((1H-imidazole-1-carbonyl)oxy)methyl)-2-nitrophenoxy)-6-(methoxycarbonyl)tetrahydro-2H-pyran-3,4,5-triyltriacetate (11).

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]
[2]Current Patent Assignee: NORTHWESTERN UNIVERSITY (ILLINOIS) - US2006/88475, 2006, A1 Location in patent: Page/Page column 8; 2 fig. 2A
[3]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2017/145044, 2017, A1 Location in patent: Paragraph 0186; 0187

10
[ 3011-34-5 ]
[ 148579-94-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 96 percent / Ag₂O / acetonitrile / 4 h 2: 96 percent / NaBH₄; silica gel; isopropanol / CHCl₃ / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: 89 percent / silver oxide / acetonitrile / 4 h / Ambient temperature 2: 99 percent / NaBH₄, silica gel HL₆₀ / CHCl₃; propan-2-ol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / Inert atmosphere 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol / Inert atmosphere

	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1.1: titanium(IV) tetrabromide / dichloromethane / 24 h / 20 °C 1.2: 4 h / 20 °C 2.1: sodium tetrahydridoborate / dichloromethane; methanol / 0.5 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 18 h / Darkness 2: isopropanol; sodium tetrahydridoborate / dichloromethane / 0 - 5 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate; mesoporous silica; isopropanol / chloroform / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate; mesoporous silica; isopropanol / chloroform / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate / chloroform; isopropanol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 18 h / Darkness 2: sodium tetrahydridoborate / dichloromethane; isopropanol / 1 h / 0 - 5 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / Molecular sieve; Inert atmosphere 2: sodium tetrahydridoborate; isopropanol / chloroform / 2.5 h / 0 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1.1: glacial acetic acid; hydrogen bromide / dichloromethane / 0 - 20 °C 1.2: 20 °C / Darkness 2.1: sodium tetrahydridoborate / isopropanol; chloroform / 0 - 20 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C / Darkness; Inert atmosphere 2: mesoporous silica; sodium tetrahydridoborate / chloroform; isopropanol / 0.75 h / 0 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 20 °C / Inert atmosphere 2: sodium tetrahydridoborate / methanol / 2 h / 20 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 5 h / 25 - 30 °C / Darkness 2: mesoporous silica; sodium tetrahydridoborate; isopropanol / dichloromethane / 2 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 18 h / 20 °C / Darkness 2: sodium tetrahydridoborate / tetrahydrofuran / 0.5 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 16 h / 20 °C 2: isopropanol; mesoporous silica; sodium tetrahydridoborate / chloroform / 1 h / 20 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]
[2]Florent, Jean-Claude; Dong, Xia; Gaudel, Gilbert; Mitaku, Sofia; Monneret, Claude; Gesson, Jean-Pierre; Jacquesy, Jean-Claude; Mondon, Martine; Renoux, Brigitte; Andrianomenjanahary, Solo; Michel, Sylvie; Koch, Michel; Tillequin, François; Gerken, Manfred; Czech, Joerg; Straub, Rainer; Bosslet, Klaus [Journal of Medicinal Chemistry, 1998, vol. 41, # 19, p. 3572 - 3581]
[3]Pettit, George R.; Arce, Pablo M.; Chapuis, Jean-Charles; Macdonald, Christian B. [Journal of Natural Products, 2015, vol. 78, # 3, p. 510 - 523]
[4]Current Patent Assignee: ABBVIE INC - WO2016/94505, 2016, A1
[5]Current Patent Assignee: UNIVERSITY OF GENEVA - WO2016/185368, 2016, A1
[6]Current Patent Assignee: ABBVIE INC - WO2016/94509, 2016, A1
[7]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2017/145044, 2017, A1
[8]Current Patent Assignee: ABBVIE INC - WO2017/214458, 2017, A2
[9]Current Patent Assignee: ABBVIE INC - WO2017/214462, 2017, A2
[10]Current Patent Assignee: ABBVIE INC - US2017/355769, 2017, A1
[11]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2018/339980, 2018, A1
[12]Current Patent Assignee: ABBVIE INC - US2019/153107, 2019, A1
[13]López Rivas, Paula; Müller, Christoph; Breunig, Christian; Hechler, Torsten; Pahl, Andreas; Arosio, Daniela; Belvisi, Laura; Pignataro, Luca; Dal Corso, Alberto; Gennari, Cesare [Organic and Biomolecular Chemistry, 2019, vol. 17, # 19, p. 4705 - 4710]
[14]Dagnæs-Hansen, Frederik; Jarlstad Olesen, Morten T.; Poier, Pier Paolo; Walther, Raoul; Zelikin, Alexander N. [Angewandte Chemie - International Edition, 2020, vol. 59, # 19, p. 7390 - 7396][Angew. Chem., 2020, vol. 132, # 19, p. 7460 - 7466,7]
[15]Anselmi, Michele; Borbély, Adina; Figueras, Eduard; Michalek, Carmela; Kemker, Isabell; Gentilucci, Luca; Sewald, Norbert [Chemistry - A European Journal, 2021, vol. 27, # 3, p. 1015 - 1022]
[16]Current Patent Assignee: ORUM THERAPEUTICS INC. - WO2021/198965, 2021, A1
[17]Current Patent Assignee: ENNOVABIO ZHEJIANG PHARMACEUTICAL; SHANGHAI ENNOVABIO PHARMACEUTICALS; ENNOVABIO ZHEJIANG PHARMACEUTICALS - CN113943312, 2022, A
[18]Ding, Kuiling; Liang, Yuru; Peng, Yingyuan; Shi, Zhixian; Wang, Yang [European Journal of Medicinal Chemistry, 2022, vol. 236]
[19]Current Patent Assignee: MERCK KGAA - WO2022/48883, 2022, A1

11
[ 148579-94-6 ]
(4S,5R,6R)-6-[4-(2-Bromo-ethylcarbamoyloxymethyl)-2-nitro-phenoxy]-4,5-dihydroxy-5,6-dihydro-4H-pyran-2-carboxylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C 3: 2.99 g / TEA / CH₂Cl₂ / 2 h / 0 °C 4: NaOMe / methanol / 1.67 h / 0 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

12
[ 148579-94-6 ]
[ 866611-70-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C 3: 2.99 g / TEA / CH₂Cl₂ / 2 h / 0 °C 4: 79 percent / NaOMe / methanol / 1.67 h / 0 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

13
[ 148579-94-6 ]
[ 870701-97-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C 3: 3.68 g / CH₂Cl₂ / 2 h / 0 - 20 °C 4: 79 percent / NaOMe / methanol / 1 h / 0 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

14
[ 148579-94-6 ]
methyl 1-(4-(2-methanesulfonyloxyethylcarbamoyloxymethyl)-2-nitrophenyl)-β-D-glucopyronuronate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C 3: 3.68 g / CH₂Cl₂ / 2 h / 0 - 20 °C 4: 79 percent / NaOMe / methanol / 1 h / 0 °C 5: 72 percent / Et₃N; DMAP; pyridine / 2 h / 0 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

15
[ 148579-94-6 ]
[ 866611-67-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C 3: 2.99 g / TEA / CH₂Cl₂ / 2 h / 0 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

16
[ 148579-94-6 ]
[ 870701-96-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C 3: 3.68 g / CH₂Cl₂ / 2 h / 0 - 20 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

17
[ 148579-94-6 ]
[ 866611-74-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C 3: 2.99 g / TEA / CH₂Cl₂ / 2 h / 0 °C 4: 79 percent / NaOMe / methanol / 1.67 h / 0 °C 5: dimethylsulfoxide / 20 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

18
[ 148579-94-6 ]
(2S,3S,4S,5R,6S)-3,4,5-Trihydroxy-6-{2-nitro-4-[2-(4,7,10-tris-carboxymethyl-1,4,7,10-tetraaza-cyclododec-1-yl)-ethylcarbamoyloxymethyl]-phenoxy}-tetrahydro-pyran-2-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C 3: 2.99 g / TEA / CH₂Cl₂ / 2 h / 0 °C 4: 79 percent / NaOMe / methanol / 1.67 h / 0 °C 5: dimethylsulfoxide / 20 °C 6: 510 mg / K₂CO₃ / acetone / 48 h / 20 °C 7: aq. NaOH / 1.25 h / 0 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

19
[ 148579-94-6 ]
Trifluoro-methanesulfonate1-methyl-3-[3-nitro-4-((2S,3R,4S,5S,6S)-3,4,5-triacetoxy-6-methoxycarbonyl-tetrahydro-pyran-2-yloxy)-benzyloxycarbonyl]-3H-imidazol-1-ium; [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

20
[ 148579-94-6 ]
methyl 1-(4-(2-(1-(4,7,10-trisethylcarboxymethyl-(1,4,7,10-tetraazacyclododecyl)))ethylcarbamoyloxymethyl)-2-nitrophenyl)-β-D-glucopyronuronate hydrobromide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 94 percent / DMAP / CH₂Cl₂ 2: CH₂Cl₂ / 0.5 h / 0 °C 3: 2.99 g / TEA / CH₂Cl₂ / 2 h / 0 °C 4: 79 percent / NaOMe / methanol / 1.67 h / 0 °C 5: dimethylsulfoxide / 20 °C 6: 510 mg / K₂CO₃ / acetone / 48 h / 20 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]

21
[ 21085-72-3 ]
[ 148579-94-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 96 percent / Ag₂O / acetonitrile / 4 h 2: 96 percent / NaBH₄; silica gel; isopropanol / CHCl₃ / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: 89 percent / silver oxide / acetonitrile / 4 h / Ambient temperature 2: 99 percent / NaBH₄, silica gel HL₆₀ / CHCl₃; propan-2-ol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: mesoporous silica; sodium tetrahydridoborate / isopropanol; chloroform / 1 h / 0 °C

	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / Inert atmosphere 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol / Inert atmosphere
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 18 h / Darkness 2: isopropanol; sodium tetrahydridoborate / dichloromethane / 0 - 5 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate / chloroform; isopropanol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 20 °C / Molecular sieve; Darkness 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 18 h / Darkness 2: sodium tetrahydridoborate / dichloromethane; isopropanol / 1 h / 0 - 5 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 6 h / 0 - 20 °C 2: sodium tetrahydridoborate; triethylamine; mesoporous silica; isopropanol / chloroform / 2 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol / 0.75 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 12 h / 20 °C / Schlenk technique; Inert atmosphere; Molecular sieve; Darkness 2: sodium tetrahydridoborate; mesoporous silica / chloroform; isopropanol / 0 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / Darkness 2: sodium tetrahydridoborate / dichloromethane / 1.17 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 4 h / 20 °C / Darkness; Inert atmosphere 2: mesoporous silica; sodium tetrahydridoborate / chloroform; isopropanol / 0.75 h / 0 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 20 °C / Inert atmosphere 2: sodium tetrahydridoborate / methanol / 2 h / 20 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 5 h / 25 - 30 °C / Darkness 2: mesoporous silica; sodium tetrahydridoborate; isopropanol / dichloromethane / 2 h / 0 °C
	Multi-step reaction with 2 steps 1.1: sodium hydroxide; benzyl-triethyl-ammonium chloride / chloroform / 16 h / 20 °C 2.1: mesoporous silica / dichloromethane; isopropanol / 0.5 h / 0 °C 2.2: 1 h / 0 °C
	Multi-step reaction with 2 steps 1: silver(I) oxide / acetonitrile / 16 h / 20 °C 2: isopropanol; mesoporous silica; sodium tetrahydridoborate / chloroform / 1 h / 20 °C

Reference： [1]Duimstra, Joseph A.; Femia, Frank J.; Meade, Thomas J. [Journal of the American Chemical Society, 2005, vol. 127, # 37, p. 12847 - 12855]
[2]Florent, Jean-Claude; Dong, Xia; Gaudel, Gilbert; Mitaku, Sofia; Monneret, Claude; Gesson, Jean-Pierre; Jacquesy, Jean-Claude; Mondon, Martine; Renoux, Brigitte; Andrianomenjanahary, Solo; Michel, Sylvie; Koch, Michel; Tillequin, François; Gerken, Manfred; Czech, Joerg; Straub, Rainer; Bosslet, Klaus [Journal of Medicinal Chemistry, 1998, vol. 41, # 19, p. 3572 - 3581]
[3]Current Patent Assignee: ACADEMIA SINICA - WO2011/66418, 2011, A1
[4]Pettit, George R.; Arce, Pablo M.; Chapuis, Jean-Charles; Macdonald, Christian B. [Journal of Natural Products, 2015, vol. 78, # 3, p. 510 - 523]
[5]Current Patent Assignee: ABBVIE INC - WO2016/94505, 2016, A1
[6]Current Patent Assignee: ABBVIE INC - WO2016/94509, 2016, A1
[7]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2017/145044, 2017, A1
[8]Current Patent Assignee: ABBVIE INC - US2017/355769, 2017, A1
[9]Walther, Raoul; Nielsen, Signe Maria; Christiansen, Rikke; Meyer, Rikke L.; Zelikin, Alexander N. [Journal of Controlled Release, 2018, vol. 287, p. 94 - 102]
[10]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2018/339980, 2018, A1
[11]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2018/339990, 2018, A1
[12]Current Patent Assignee: ABBVIE INC - US2019/153107, 2019, A1
[13]Walther, Raoul; Jarlstad Olesen, Morten T.; Zelikin, Alexander N. [Organic and Biomolecular Chemistry, 2019, vol. 17, # 29, p. 6970 - 6974]
[14]Current Patent Assignee: IL 2RX - WO2020/14541, 2020, A2
[15]Anselmi, Michele; Borbély, Adina; Figueras, Eduard; Michalek, Carmela; Kemker, Isabell; Gentilucci, Luca; Sewald, Norbert [Chemistry - A European Journal, 2021, vol. 27, # 3, p. 1015 - 1022]
[16]Current Patent Assignee: ORUM THERAPEUTICS INC. - WO2021/198965, 2021, A1
[17]Current Patent Assignee: ENNOVABIO ZHEJIANG PHARMACEUTICAL; SHANGHAI ENNOVABIO PHARMACEUTICALS; ENNOVABIO ZHEJIANG PHARMACEUTICALS - CN113943312, 2022, A
[18]Calatrava-Pérez, Elena; Elmes, Robert B. P.; Gunnlaugsson, Thorfinnur; Lynch, Dylan M.; Marchetti, Luke A.; McManus, Gavin J.; Scanlan, Eoin M.; Williams, D. Clive [Chemistry - A European Journal, 2022, vol. 28, # 3]
[19]Current Patent Assignee: MERCK KGAA - WO2022/48883, 2022, A1

22
[ 148579-94-6 ]
O⁶-benzyl-N²-[[[[4'-[(β-D-glucopyranuronosyl)oxy]-3'-nitrophenyl]methyl]oxy]carbonyl]guanine monosodium salt [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: pyridine / CH₂Cl₂; toluene / 20 h 1.2: 42 percent / CH₂Cl₂; toluene / 2 h / 20 °C 2.1: 64 percent / aq. NaOH / methanol / 0.5 h / 0 °C

Reference： [1]Wei, Guangping; Loktionova, Natalia A.; Pegg, Anthony E.; Moschel, Robert C. [Journal of Medicinal Chemistry, 2005, vol. 48, # 1, p. 256 - 261]

23
[ 148579-94-6 ]
[ 637330-34-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 65 percent / NaOMe / methanol / -15 - 20 °C 2: 85 percent / imidazole / dimethylformamide / 8 h / 20 °C

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

24
[ 148579-94-6 ]
[ 637330-37-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: 65 percent / NaOMe / methanol / -15 - 20 °C 2: 85 percent / imidazole / dimethylformamide / 8 h / 20 °C 3: 84 percent / DMAP / pyridine; CH₂Cl₂ / 20 °C 4: 72 percent / Ti(OEt)4; 4 Angstroem molecular sieves / toluene / 48 h / Heating 5: 85 percent / AcOH; TBAF / dimethylformamide

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

25
[ 148579-94-6 ]
methyl [2-nitro-4-(O-tert-butyldimethylsilylmethyl)phenyl]-2,3,4-tri-(O-tert-butyldimethylsilyl)-β-D-glucopyranosid}uronate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: 65 percent / NaOMe / methanol / -15 - 20 °C 2.1: DMAP; imidazole / dimethylformamide / 48 h / 80 °C 2.2: 85 percent / DMAP; pyridine / dimethylformamide / 20 °C

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

26
[ 148579-94-6 ]
(2S,3R,4S,5R,6S)-3,4,5-Tris-(tert-butyl-dimethyl-silanyloxy)-6-[4-(tert-butyl-dimethyl-silanyloxymethyl)-2-nitro-phenoxy]-tetrahydro-pyran-2-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: aq. NaOH / acetone / 0.08 h / 0 °C 2: DMAP; pyridine / 18 h / 20 °C

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

27
[ 148579-94-6 ]
benzyl [2-nitro-4-(O-tert-butyldimethylsilylmethyl)phenyl]-2,3,4-tri-(O-tert-butyldimethylsilyl)-β-D-glucopyranosid}uronate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: aq. NaOH / acetone / 0.08 h / 0 °C 2: DMAP; pyridine / 18 h / 20 °C 3: 230 mg / DCC; DMAP / CH₂Cl₂

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

28
[ 148579-94-6 ]
[ 637330-35-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 65 percent / NaOMe / methanol / -15 - 20 °C 2: 85 percent / imidazole / dimethylformamide / 8 h / 20 °C 3: 84 percent / DMAP / pyridine; CH₂Cl₂ / 20 °C

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

29
[ 148579-94-6 ]
[ 637330-38-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 65 percent / NaOMe / methanol / -15 - 20 °C 2: 85 percent / imidazole / dimethylformamide / 8 h / 20 °C 3: 84 percent / DMAP / pyridine; CH₂Cl₂ / 20 °C 4: 72 percent / Ti(OEt)4; 4 Angstroem molecular sieves / toluene / 48 h / Heating 5: 85 percent / AcOH; TBAF / dimethylformamide 6: 54 percent / pyridine / CH₂Cl₂ / 20 °C

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

30
[ 148579-94-6 ]
[ 637330-41-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 9 steps 1: 65 percent / NaOMe / methanol / -15 - 20 °C 2: 85 percent / imidazole / dimethylformamide / 8 h / 20 °C 3: 84 percent / DMAP / pyridine; CH₂Cl₂ / 20 °C 4: 72 percent / Ti(OEt)4; 4 Angstroem molecular sieves / toluene / 48 h / Heating 5: 85 percent / AcOH; TBAF / dimethylformamide 6: 54 percent / pyridine / CH₂Cl₂ / 20 °C 7: 38 mg / pyridine / CH₂Cl₂ / 5 h / 20 °C 8: aq. HCl / ethyl acetate / 0 °C 9: 230 mg / Et₃N / toluene / 2.5 h / 0 °C

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

31
[ 148579-94-6 ]
[ 637330-39-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1: 65 percent / NaOMe / methanol / -15 - 20 °C 2: 85 percent / imidazole / dimethylformamide / 8 h / 20 °C 3: 84 percent / DMAP / pyridine; CH₂Cl₂ / 20 °C 4: 72 percent / Ti(OEt)4; 4 Angstroem molecular sieves / toluene / 48 h / Heating 5: 85 percent / AcOH; TBAF / dimethylformamide 6: 54 percent / pyridine / CH₂Cl₂ / 20 °C 7: 38 mg / pyridine / CH₂Cl₂ / 5 h / 20 °C

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

32
[ 148579-94-6 ]
[ 637330-36-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 65 percent / NaOMe / methanol / -15 - 20 °C 2: 85 percent / imidazole / dimethylformamide / 8 h / 20 °C 3: 84 percent / DMAP / pyridine; CH₂Cl₂ / 20 °C 4: 72 percent / Ti(OEt)4; 4 Angstroem molecular sieves / toluene / 48 h / Heating

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

33
[ 148579-94-6 ]
N,N'-dimethyl-N-benzyl-[4-(2,3,4-tri-O-tert-butyldimethylsilyl-β-D-glucopyranosyl)uronate-3-nitrobenzoyloxycarbonyl]ethylenediamine hydrochloride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 8 steps 1: 65 percent / NaOMe / methanol / -15 - 20 °C 2: 85 percent / imidazole / dimethylformamide / 8 h / 20 °C 3: 84 percent / DMAP / pyridine; CH₂Cl₂ / 20 °C 4: 72 percent / Ti(OEt)4; 4 Angstroem molecular sieves / toluene / 48 h / Heating 5: 85 percent / AcOH; TBAF / dimethylformamide 6: 54 percent / pyridine / CH₂Cl₂ / 20 °C 7: 38 mg / pyridine / CH₂Cl₂ / 5 h / 20 °C 8: aq. HCl / ethyl acetate / 0 °C

Reference： [1]Bouvier, Emmanuel; Thirot, Sylvie; Schmidt, Frederic; Monneret, Claude [Organic and Biomolecular Chemistry, 2003, vol. 1, # 19, p. 3343 - 3352]

34
[ 148579-94-6 ]
[ 228412-63-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: NEt₃ / acetonitrile / 2 h / 20 °C 2: Et₃N / acetonitrile; dimethylformamide / 16 h / 20 °C