Name: 4098-06-0|(2R,3R,4R)-2-(Acetoxymethyl)-3,4-dihydro-2H-pyran-3,4-diyl diacetate|95%
Brand: Ambeed
SKU: A113736
Price: 6.0 USD
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Rating: 96 (35 reviews)

1
[ 3068-32-4 ]
[ 4098-06-0 ]

Yield	Reaction Conditions	Operation in experiment
98%	With edetate disodium; chromium(II) acetate In water; ethyl acetate for 18h; Ambient temperature;
97%	With tetrakis(acetato)dichromium(II) dihydrate; edetate disodium In water; ethyl acetate for 18h;
93%	With fipronilβ-cyclodextrin; zinc In water at 20℃; for 0.5h; Sonication;

93%	With zinc; sodium acetate; acetic acid In tetrahydrofuran at 20℃; for 1.5h;
91%	With acetic acid; zinc In acetonitrile for 0.833333h;
90%	With ammonium chloride; zinc In acetonitrile at 60℃; for 4h; Alkaline conditions;
89%	With bis(cyclopentadienyl)-titanium(III) chloride In tetrahydrofuran Ambient temperature;
89%	With bis(cyclopentadienyl)-titanium(III) chloride In tetrahydrofuran for 0.25h; Ambient temperature;
88.7%	Stage #1: 1-bromo-1-deoxy-2,3,4,6-tetra-O-acetyl-a-D-galactopyranoside With ammonium chloride In acetonitrile at 20℃; Stage #2: With zinc In acetonitrile for 1.51667h;	2.b Preparation of 3,4, 6-Tri-O-acetyl-D-galactal; Ammonium chloride (30 g, 0.561 mol) was added to 2,3, 4, 6-tetra-O-acetyl-a-D- galactopyranosyl bromide (97 g, 0.236 mol) in acetonitrile (500 mL) and this reaction mixture was stirred and kept under a blanket of nitrogen at room temperature. Most of the ammonium chloride remained undissolved. Zinc powder (36 g, 0.551 mmol) was added cautiously to the mixture within 1 minute followed by VO (Salen) (0.25 g, mmol) in one batch. After an induction time of about 30 minutes, an exothermic occurred. The solution became lighter and the temperature slowly cools down. Stirring was continued for a further 60 minutes. The progress of the reaction was checked by NMR and after 60 minutes showed that the reaction had finished. Workup of this reaction mixture was carried out in the same manner as for 3,4, 6-tri-O-acetyl-D-glucal. Yield of crude 3,4, 6-tri-O-acetyl-D- galactal (57.0 g, 88. 7%). 1H-NMR (300 MHz, CDC13) : 8 : 6.388 (dd, J=6. 4,1. 4 Hz, 1H), 5.47 (m, lH), 5.349 (dm, J=4. 4 Hz, 1H), 4.672 (ddd, J=6. 3,3. 7,1. 4 Hz, 1H), 4. 268 (dd, J=5. 0,5. 0 Hz, 1H), 4.166 (dd, J=6. 1,4. 3 Hz, 1H), 4. 05 (m, 1H), 2.048, 2.005, 1. 948 (3x CH3). 13C-NMR (75 MHz, CDCl3) : 8 : 170.23, 169.96, 169.85 (3 x C=O), 98.65 (CH- 0), 72.61 (CH-O), 63.69, 63.60 (2x CH), 61.69 (CH2-O), 20.48, 20.42, 20.32 (3x CH3).
84%	With ammonium chloride; zinc In acetonitrile at 60℃; for 0.583333h; Inert atmosphere;	2. General procedure for the synthesis of glycals General procedure: Under nitrogen, the glycopyranosyl bromide (1.0 mmol) was dissolved in CH3CN, and then zinc dust (7.5 mmol) and ammonium chloride (7.5 mmol) were added, followed by stirring at corresponding temperature. Upon completion of the reaction (monitored by TLC), inorganic salts and excessive zinc dust were removed by filtration. The filtrate was concentrated in vacuo and the residue was purified by silica gel flash column chromatography to afford the corresponding glycal in pure form.
81%	With sodium dihydrogenphosphate; zinc In acetone at 20℃; for 5h;
80%	With zinc In water at 20℃; for 1h;
78.7%	With 1-methyl-1H-imidazole; zinc In ethyl acetate Heating;
77%	In tetrahydrofuran at 20℃;
77%	With manganese; chloro-trimethyl-silane In tetrahydrofuran at 20℃; for 12h;
77%	With 1-methyl-1H-imidazole; zinc In ethyl acetate Heating;
72%	With 1-methyl-1H-imidazole; zinc In ethyl acetate for 3h; Reflux;
71%	With <Cr(II)(EDTA)>(2-) In water; N,N-dimethyl-formamide for 432h; pH 5.0;
70%	With copper(II) sulfate; zinc In water; acetic acid at 20℃;
60%	With aluminium amalgam In tetrahydrofuran; water for 4h; Ambient temperature;
60%	With copper(ll) sulfate pentahydrate; sodium acetate; zinc In water; acetic acid at 0℃; for 3.25h; Inert atmosphere;
48%	With lithium perchlorate In tetrahydrofuran Electrochemical reaction;
	With acetic acid; zinc
	With 1-methyl-1H-imidazole; zinc In ethyl acetate for 0.416667h; Heating; Yield given;
	With 1-methyl-1H-imidazole; zinc In ethyl acetate for 2h; Heating;
7.76 g	With copper(II) sulfate; zinc In water; acetic acid at 20℃; for 18h;
2.54 g	With acetic acid; zinc In water at 0℃;
27.7 g	With acetic acid; zinc In diethyl ether; water at 0℃; for 1h; Inert atmosphere;	D-Galactal Using a modification of Kozikowski’s procedure,1 a magnetically stirred solution of D-galactose (S2, 125 mg, 0.7 mmol) in acetic anhydride (75 mL, 790 mmol) was treated dropwise with conc. perchloric acid (0.45 mL, 6.9 mmol). The remaining D-galactose (19.9 g, 110.3 mmol) was slowly added over 30 minutes, at a rate that maintained a temperature of 40-50 °C. Upon complete addition of D-galactose, the solution was allowed to cool to room temperature, then treated with a 33% (w/w) solution of hydrobromic acid in acetic acid (75 mL, 410 mmol). After 90 minutes, the solution was diluted with dichloromethane (180 mL) and washed with ice-cold water (2 x 50 mL), then with cold saturated sodium bicarbonate solution (4 x 100 mL). The organic phase was dried, filtered and concentrated to afford crude tetra-O-acetyl-α-D-galactopyranosyl bromide as a pale-yellow oil.A mechanically stirred dispersion of zinc dust (48.0 g, 734 mmol) in water (150 mL) was cooled to 0 °C, diluted with acetic acid (150 mL), then treated dropwise over one hour with a solution of tetra-O-acetyl-α-D-galactopyranosyl bromide in diethyl ether (150 mL). The reaction was allowed to warm to room temperature and left to proceed overnight. The solution was filtered, then diluted with dichloromethane (200 mL). The solution was then washed successively with water (3 x 60 mL), saturated sodium bicarbonate solution (3 x 50 mL) and brine (60 mL). The organic phase was dried, filtered and concentrated to provide tri-O-acetyl-D-galactal (S5) (27.7 g) as a pale-yellow oil.
24.424 g	With copper(II) sulfate; zinc In acetic acid at 25℃; for 0.583333h; Inert atmosphere;
5.40 g	With sodium dihydrogenphosphate; zinc In acetone at 20℃; Inert atmosphere;	4.7 3,4,6-Tri-O-acetyl-D-galactal (11) To a solution of compound 10 (9.20g, 22.37mmol) in acetone (44.4mL) was added saturated NaH2PO4 solution (89.5mL) and zinc dust (18.29g, 279.63mmol). The reaction mixture was stirred at the room temperature for overnight. The mixture was then diluted with EtOAc and filtered through a pad of celite, then concentrated to dryness in vacuum. The residue was diluted with EtOAc (500mL), washed with saturated NaHCO3(aq) (100mL×2), water (100mL), and brine (100mL). The organic layer was dried over MgSO4 and concentrated to give a crude product, which was purified by flash chromatography with the eluent of EtOAc/hexanes=3/7 to give the desired product 11 (5.40g, 89%) as a colorless oil. 1H NMR (300MHz, CDCl3) δ 6.46 (dd, J=6.3, 1.5Hz, 1H), 5.58-5.53 (m, 1H), 5.42 (dt, J=4.8, 1.7Hz, 1H), 4.73 (ddd, J=6.3, 2.9, 1.7Hz, 1H), 4.35-4.17 (m, 3H), 2.13 (s, 3H), 2.08 (s, 3H), 2.03 (s, 3H); 13C NMR (75MHz, CDCl3) δ 170.6 (C), 170.1 (C), 170.3 (C), 170.1 (C), 145.4 (CH), 98.8 (CH), 72.8 (CH), 63.8 (CH), 63.7 (CH), 61.9 (CH2), 20.8 (CH3), 20.7 (CH3), 20.6 (CH3).
	With acetic acid; zinc In water at 0 - 20℃;

Reference： [1]Kovacs, Gyoengyver; Gyarmati, Julianna; Somsak, Laszlo; Micskei, Karoly [Tetrahedron Letters, 1996, vol. 37, # 8, p. 1293 - 1296]
[2]Kovacs, Gyoengyver; Micskei, Karoly; Somsak, Laszlo [Carbohydrate Research, 2001, vol. 336, # 3, p. 225 - 228]
[3]Location in patent: experimental part Zhao, Jinzhong; Shao, Huawu; Wu, Xin; Shi, Shaojing [Chinese Journal of Chemistry, 2011, vol. 29, # 7, p. 1434 - 1440]
[4]Xu, Yun; Wang, Wenjun; Cai, Yu; Yang, Xia; Wang, Peng George; Zhao, Wei [RSC Advances, 2014, vol. 4, # 87, p. 46662 - 46665]
[5]Stick, Robert V.; Stubbs, Keith A.; Tilbrook, D. Matthew G.; Watts, Andrew G. [Australian Journal of Chemistry, 2002, vol. 55, # 1-2, p. 83 - 85]
[6]Chapa-Villarreal, Fabiola A.; Chiaramonte, Jonathan; Piazza, Sabrina M.; Reynolds, Michael R.; Trant, John F.; Xu, Peihan [New Journal of Chemistry, 2021, vol. 45, # 41, p. 19224 - 19227]
[7]Cavallaro, Cullen L.; Schwartz, Jeffrey [Journal of Organic Chemistry, 1995, vol. 60, # 21, p. 7055 - 7057]
[8]Spencer, Roxanne P.; Cavallaro, Cullen L.; Schwartz, Jeffrey [Journal of Organic Chemistry, 1999, vol. 64, # 11, p. 3987 - 3995]
[9]Current Patent Assignee: MONASH UNIVERSITY - WO2005/70911, 2005, A1 Location in patent: Page/Page column 39-40
[10]Chen, Heshan; Xian, Ting; Zhang, Wan; Si, Wenshuai; Luo, Xiaosheng; Zhang, Bo; Zhang, Meiyu; Wang, Zhongfu; Zhang, Jianbo [Carbohydrate Research, 2016, vol. 431, p. 42 - 46]
[11]Location in patent: experimental part Zhao, Jinzhong; Wei, Shanqiao; Ma, Xiaofeng; Shao, Huawu [Carbohydrate Research, 2010, vol. 345, # 1, p. 168 - 171]
[12]Location in patent: experimental part Zhao, Jinzhong; Wei, Shanqiao; Ma, Xiaofeng; Shao, Huawu [Green Chemistry, 2009, vol. 11, # 8, p. 1124 - 1127]
[13]Bukowski, Ralph; Morris, Laura M.; Woods, Robert J.; Weimar, Thomas [European Journal of Organic Chemistry, 2001, # 14, p. 2697 - 2705]
[14]Hansen, Thomas; Krintel, Sussie L.; Daasbjerg, Kim; Skrydstrup, Troels [Tetrahedron Letters, 1999, vol. 40, # 33, p. 6087 - 6090]
[15]Hansen; Daasbjerg; Skrydstrup [Tetrahedron Letters, 2000, vol. 41, # 44, p. 8645 - 8649]
[16]Location in patent: scheme or table Balcerzak, Anna K.; Ferreira, Sandra S.; Trant, John F.; Ben, Robert N. [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 4, p. 1719 - 1721]
[17]Location in patent: experimental part Lee, Dong Jun; Harris, Paul W.R.; Kowalczyk, Renata; Dunbar, P. Rod; Brimble, Margaret A. [Synthesis, 2010, # 5, p. 763 - 769]
[18]Kovacs, Gyoengyver; Toth, Krisztina; Dinya, Zoltan; Somsak, Laszlo; Micskei, Karoly [Tetrahedron, 1999, vol. 55, # 16, p. 5253 - 5264]
[19]Mitchell; Pratt; Hruby; Polt [Journal of Organic Chemistry, 2001, vol. 66, # 7, p. 2327 - 2342]
[20]Jain, Sudha; Suryawanshi, S. N.; Bhakuni, D. S. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1987, vol. 26, # 1-12, p. 866 - 867]
[21]Chabre, Yoann M.; Giguere, Denis; Blanchard, Bertrand; Rodrigue, Jacques; Rocheleau, Sylvain; Neault, Mathieu; Rauthu, Subhash; Papadopoulos, Alex; Arnold, Alexandre A.; Imberty, Anne; Roy, Rene [Chemistry - A European Journal, 2011, vol. 17, # 23, p. 6545 - 6562]
[22]Parrish; Little [Tetrahedron Letters, 2001, vol. 42, # 42, p. 7371 - 7374]
[23]Levene; Tipson [Journal of Biological Chemistry, 1931, vol. 93, p. 631,634, 635] Overend et al. [Journal of the Chemical Society, 1950, p. 671,676][Journal of the Chemical Society, 1951, p. 992,993]
[24]Broddefalk, Johan; Nilsson, Ulf; Kihlberg, Jan [Journal of Carbohydrate Chemistry, 1994, vol. 13, # 1, p. 129 - 132]
[25]Bay, Sylvie; Huteau, Valérie; Zarantonelli, Maria-Leticia; Pires, René; Ughetto-Monfrin, Joël; Taha, Muhamed-Kheir; England, Patrick; Lafaye, Pierre [Journal of Medicinal Chemistry, 2004, vol. 47, # 16, p. 3916 - 3919]
[26]Kasuya, Maria Carmelita; Ito, Ayaka; Hatanaka, Kenichi [Journal of Fluorine Chemistry, 2007, vol. 128, # 5, p. 562 - 565]
[27]Rempel; Withers [Organic and Biomolecular Chemistry, 2014, vol. 12, # 16, p. 2592 - 2595]
[28]Moore, Peter W.; Schuster, Julia K.; Hewitt, Russell J.; Stone, M. Rhia L.; Teesdale-Spittle, Paul H.; Harvey, Joanne E. [Tetrahedron, 2014, vol. 70, # 39, p. 7032 - 7043]
[29]Keith, D. Jamin; Townsend, Steven D. [Journal of the American Chemical Society, 2019, vol. 141, # 32, p. 12939 - 12945]
[30]Liu, Si-Xian; Tsai, Yun-Tzu; Lin, Yu-Tung; Li, Jia-Yue; Chang, Che-Chien [Tetrahedron, 2019, vol. 75, # 52]
[31]Chang, Chun-Wei; Wu, Chia-Hui; Lin, Mei-Huei; Liao, Pin-Hsuan; Chang, Chun-Chi; Chuang, Hsiao-Han; Lin, Su-Ching; Lam, Sarah; Verma, Ved Prakash; Hsu, Chao-Ping; Wang, Cheng-Chung [Angewandte Chemie - International Edition, 2019, vol. 58, # 47, p. 16775 - 16779][Angew. Chem., 2019, vol. 131, # 47, p. 16931 - 16935,5]

3
[ 60511-85-5 ]
[ 4098-06-0 ]
[ 160137-65-5 ]
C₂₇H₂₂N₂O₆ [ No CAS ]
C₂₇H₂₂N₂O₆ [ No CAS ]

Reference： [1]Tetrahedron Letters,1994,vol. 35,p. 3005 - 3008

4
[ 1666-13-3 ]
[ 4098-06-0 ]
[ 150809-76-0 ]

Yield	Reaction Conditions	Operation in experiment
97%	With [bis(acetoxy)iodo]benzene; trimethylsilylazide In dichloromethane at -30 - 20℃; for 12h;
92%	With sodium azide; [bis(acetoxy)iodo]benzene In dichloromethane for 48h; Ambient temperature;
92%	With sodium azide; [bis(acetoxy)iodo]benzene In dichloromethane for 48h; Ambient temperature;

92%	With sodium azide; [bis(acetoxy)iodo]benzene In dichloromethane at 20℃;
87%	With sodium azide; [bis(acetoxy)iodo]benzene In dichloromethane for 192h; Ambient temperature;
82%	With sodium azide; [bis(acetoxy)iodo]benzene
81%	With sodium azide; [bis(acetoxy)iodo]benzene In dichloromethane at 20℃; for 48h;
72%	With [bis(acetoxy)iodo]benzene; trimethylsilylazide In dichloromethane at -30 - 20℃; for 3h; Inert atmosphere;	Phenyl 2-azido-3,4,6-tri-O-acetyl-2-deoxy-1-seleno-a-D-galactopyranoside (8). D-Galactal 7[48] (2.0 g, 7.35 mmol) was dissolved in anhydrous DCM(35 mL) and cooled to 30 C under argon. Diphenyl diselenide (2.3 g,7.37 mmol), (diacetoxyliodo) benzene (BAIB) (2.4 g, 7.45 mmol) and trimethylsilylazide (1.8 mL, 13.69 mmol) were added. The solution was thenallowed to warm to room temperature for 3 h. After the complete conversionof the starting material, the solution was extracted with satd. aq.NaHCO3 (320 mL), combined the organic layer and dried over Na2SO4.The solvent was removed under vacuum and the residue was purified bysilica gel column chromatography (petroleum ether: ethyl acetate 6: 1 v/v)to give compound 8 (2.5 g, 5.32 mmol, 72%). [a]D20 931.7 (c1.00,CHCl3); 1H NMR (400 MHz, CDCl3) d7.787.11 (m, 5H, Ar-H), 6.01(d, J5.4 Hz, 1H, 1-H), 5.47 (dd, J3.4, 1.4 Hz, 1H, 4-H), 5.12 (dd,J10.9, 3.3 Hz, 1H, 3-H), 4.67 (ddd, J7.1, 5.8, 1.3 Hz, 1H, 5-H), 4.26(dd, J10.9, 5.4 Hz, 1H, 2-H), 4.08 (dd, J11.5, 5.9 Hz, 1H, 6-CH2), 4.02(dd, J11.4, 7.1 Hz, 1H, 6-CH2), 2.15 (s, 3H, COCH3), 2.07 (s, 3H,COCH3), 1.98 (s, 3H, COCH3); 13C NMR (100 MHz, CDCl3): d170.4,170.0, 169.7, 134.9, 129.3, 128.3, 127.7, 84.2, 71.3, 69.1, 67.3, 61.6, 58.8,29.8, 20.74, 20.71.
70%	With sodium azide; [bis(acetoxy)iodo]benzene In dichloromethane for 48h; Ambient temperature;
70%	With sodium azide; [bis(acetoxy)iodo]benzene In dichloromethane for 48h; Ambient temperature;
70%	With [bis(acetoxy)iodo]benzene; trimethylsilylazide In dichloromethane at -30 - 20℃; for 3.5h; Inert atmosphere;	3 Galactene compound 8 (2.0 g, 7.35 mmol)Soluble in anhydrous dichloromethane (35ml),It was then cooled to -30 °C.Add iodobenzene diacetate (2.4 g, 7.35 mmol) under argon protectionAnd azide trimethylsilane (1.8ml, 14.7mmol),Continue to stir at -30 ° C for 0.5 h,Then slowly return to room temperature,After stirring for 3 h, the reaction of the starting material was completely monitored by TLC.The reaction was washed three times with saturated NaHCO3 (20 mL).The organic layer was separated and dried over anhydrous sodium sulfate, filtered, and then evaporated.Compound 9 (2.4 g, 5.15 mmol, 70%) was obtained.
	With [bis(acetoxy)iodo]benzene; triethylsilyl azide at -10℃; for 16h;
58 %Spectr.	With [bis(acetoxy)iodo]benzene; trimethylsilylazide In dichloromethane at 27℃; for 0.416667h; Flow reactor;
	With [bis(acetoxy)iodo]benzene; trimethylsilylazide In dichloromethane at -30 - -18℃;

Reference： [1]Kikkeri, Raghavendra; Lepenies, Bernd; Adibekian, Alexander; Laurino, Paola; Seeberger, Peter H. [Journal of the American Chemical Society, 2009, vol. 131, p. 2110 - 2112]
[2]Czernecki, S.; Ayadi, E.; Randriamandimby, D. [Journal of Organic Chemistry, 1994, vol. 59, # 26, p. 8256 - 8260]
[3]Czernecki; Ayadi [Canadian Journal of Chemistry, 1995, vol. 73, # 3, p. 343 - 350]
[4]Fomitskaya, Polina A.; Argunov, Dmitry A.; Tsvetkov, Yury E.; Lalov, Andrey V.; Ustyuzhanina, Nadezhda E.; Nifantiev, Nikolay E. [European Journal of Organic Chemistry, 2021, vol. 2021, # 44, p. 5897 - 5904]
[5]Santoyo-Gonzalez, F.; Calvo-Flores, F. G.; Garcia-Mendoza, P.; Hernandez-Mateo, F.; Isac-Garcia, J.; Robles-Diaz, R. [Journal of Organic Chemistry, 1993, vol. 58, # 22, p. 6122 - 6125]
[6]Sanmartin, Raul; Tavassoli, Bahareh; Walsh, Kenneth E.; Walter, Daryl S.; Gallagher, Timothy [Organic Letters, 2000, vol. 2, # 25, p. 4051 - 4054]
[7]Jiaang, Weir-Torn; Chang, Meng-Yang; Tseng, Ping-Hui; Chen, Shui-Tein [Tetrahedron Letters, 2000, vol. 41, # 17, p. 3127 - 3130]
[8]Qin, Chunjun; Liu, Zhonghua; Ding, Meiru; Cai, Juntao; Fu, Junjie; Hu, Jing; Seeberger, Peter H.; Yin, Jian [Journal of Carbohydrate Chemistry, 2020, vol. 39, # 8, p. 374 - 397]
[9]Czernecki, Stanislas; Ayadi, Ebtissam; Randriamandimby, Dominique [Journal of the Chemical Society. Chemical communications, 1994, # 1, p. 35 - 36]
[10]Czernecki; Randriamandimby [Tetrahedron Letters, 1993, vol. 34, # 49, p. 7915 - 7916]
[11]Current Patent Assignee: JIANGNAN UNIVERSITY - CN109627270, 2019, A Location in patent: Paragraph 0061; 0065
[12]Location in patent: experimental part Mironov, Yu. V.; Grachev; Lalov; Sherman; Egorov; Nifantiev [Russian Chemical Bulletin, 2009, vol. 58, # 2, p. 284 - 290]
[13]Guberman, Mónica; Pieber, Bartholomäus; Seeberger, Peter H. [Organic Process Research and Development, 2019, vol. 23, # 12, p. 2764 - 2770]
[14]Kazakova, Ekaterina D.; Yashunsky, Dmitry V.; Krylov, Vadim B.; Bouchara, Jean-Philippe; Cornet, Murielle; Valsecchi, Isabel; Fontaine, Thierry; Latgé, Jean-Paul; Nifantiev, Nikolay E. [Journal of the American Chemical Society, 2020, vol. 142, # 3, p. 1175 - 1179]

5
[ 100-39-0 ]
[ 4098-06-0 ]
[ 80040-79-5 ]

Yield	Reaction Conditions	Operation in experiment
64%		Tri-O-acetyl-galactal 25 (10.0 g, 36.7 mmol) wasdissolved in 20 mL THF and finely crushed NaOH (17.0 g,0.425 mol) was added. The reaction mixture was left for 3 hat room temperature. Tetra-n-butylammonium iodide(TBAI) (2.0 g, 6.0 mumol) and benzylbromide (15 mL, 0.13mol) were added to the reaction and the reaction mixturewas left to stir for 12 h. TLC analysis indicated the completionof the reaction, which was then quenched with waterand the organic layer was extracted with ethyl acetate,washed with water and dried over MgSO4. After filtration,the solvent was removed under reduced pressure and a lightyellow oil appeared. This was purified by column chromatographyon silica gel using hexane and ethyl acetate.(5:1) as eluent to provide the title compound 26: yellow oil,64% (9.97 g); 1H NMR (400MHz, CDCl3) delta: 7.24-7.15 (m,15H, Ar), 6.26 (dd, J = 1.2 and 6.4 Hz, 1H, H-1), 4.82-4.74(m, 2H, H-2, and -OCHAHBPh), 4.57-4.50 (m, 3H,3 × -OCHAHBPh), 4.39 (d, J = 12.0 Hz, 1H,-OCHAHBPh), 4.31 (d, J = 11.6 Hz, 1H, -OCHAHBPh), 4.10-4.02 (m, 2H, H-4, and H-5), 3.85-3.83 (m, 1H, H-3),3.67 (dd, J = 7.4 and 10.2 Hz, 1H, H-6a), 3.53 (dd, J = 5.2and 10.0 Hz, 1H, H-6b); 13C NMR (100 MHz, CDCl3) delta:128.5, 128.4, 128.3, 128.0, 127.3, 127.2, 126.8, 126.7,126.6 (Ar), 77.9 (C-3), 74.5 (C-4), 73.6 (-OCH2Ph), 72.1(-OCH2Ph), 71.5 (-OCH2Ph), 71.0 (C-6), 69.1 (C-5), 61.5(C-1), 58.4 (C-2). The spectroscopic data were in agreementwith the literature report (Fischer and Hamann 1995).
		FIGURE 44 shows the synthesis of compound MIF- 18-3, Tri-acyl galactal was deprotected with ammonia in methanol, then tri-benzyl protected with benzylbromide in the presence of base. The alkene was hydrolyzed overnight with HC1 in THF/H20, then oxidized with PCC to give an aldehyde. Sodium azide was then added alpha to the carbonyl with KHMDS and TIBSN3 at lowered temperature. The intermediated was then treated with p- OMePhMgBr in THF and toluene to give an intermediate alcohol, which was then reduced using Et3SiH in the presence of BF3-Et20 at reduced temperature. The resulting azide was then reduced with Lindlar?s catalyst under a hydrogen atmosphere to give the corresponding amine, which was acylated with trifluoroacetic acid in pyridine. The benzyl groups were then removed with Pd(OH2) on carbon in MeOH at reflux, and the resulting tri-ol protected as an acetal with dimethoxypropane and camphorsulfonic acid at elevated temperature. The remainder of the synthesis was carried out as described for previous molecules.

Reference： [1]Carbohydrate Research,2005,vol. 340,p. 1373 - 1377
[2]Organic and Biomolecular Chemistry,2018,vol. 16,p. 5107 - 5112
[3]Medicinal Chemistry Research,2018,vol. 27,p. 817 - 833
[4]Tetrahedron,1989,vol. 45,p. 227 - 232
[5]Bioorganic Chemistry,2007,vol. 35,p. 401 - 416
[6]Chemistry - A European Journal,2018,vol. 24,p. 16266 - 16270
[7]Patent: WO2019/199634,2019,A1 .Location in patent: Page/Page column 73

6
[ 118358-66-0 ]
[ 4098-06-0 ]
[ 109978-00-9 ]

Reference： [1]Angewandte Chemie,1987,vol. 99,p. 919 - 921

7
[ 73724-48-8 ]
[ 4098-06-0 ]
[ 109995-89-3 ]

Reference： [1]Liebigs Annalen der Chemie,1991,p. 727 - 744
[2]Angewandte Chemie,1987,vol. 99,p. 919 - 921

8
[ 73724-46-6 ]
[ 4098-06-0 ]
3-((2S,3R,4S,5S,6R)-4,5-Diacetoxy-6-acetoxymethyl-3-iodo-tetrahydro-pyran-2-yloxy)-2-(9H-fluoren-9-ylmethoxycarbonylamino)-propionic acid benzyl ester [ No CAS ]
[ 109978-00-9 ]

Reference： [1]Liebigs Annalen der Chemie,1991,p. 727 - 744

9
[ 108-98-5 ]
[ 4098-06-0 ]
[ 125848-19-3 ]

Yield	Reaction Conditions	Operation in experiment
96%	With tin(IV) chloride In dichloromethane at -20℃;
96%	With tin(IV) chloride In dichloromethane
86%	With carbon immobilized iron (III) chloride hexahydrate In dichloromethane at 20℃; for 0.5h; stereoselective reaction;	General Experimental Procedure for the Synthesis of2,3-Unsaturated Galactosides General procedure: To a stirred solution of tri-O-acetyl-D-galactal (50 mg, 0.185 mmol) in DCM(1 mL) were added the corresponding alcohol (0.204 mmol, 1.1 equiv) andFeCl3·6H2O/C (50 mol%) at ambient temperature. After the reaction was completed(monitored by TLC), the reaction mixture was filtered and the catalystwas washed with dichloromethane. After evaporation of the solvent under vacuum,the crude products were purified by silica gel column chromatography(petroleum ether/EtOAc = 10/1).

66%	With tin(IV) chloride In dichloromethane at -20℃; for 1h;
	With boron trifluoride diethyl etherate In dichloromethane at -78℃;

Reference： [1]Halcomb, Randall L.; Wittman, Mark D.; Olson, Steven H.; Danishefsky, Samuel J.; Golik, Jerzy; Wong, Henry; Vyas, Dolatrai [Journal of the American Chemical Society, 1991, vol. 113, # 13, p. 5080 - 5082]
[2]Danishefsky, Samuel J.; Shair, Matthew D. [Journal of Organic Chemistry, 1996, vol. 61, # 1, p. 16 - 44]
[3]Zhou, Jiafen; Chen, Heshan; Shan, Junjie; Li, Juan; Yang, Guofang; Chen, Xuan; Xin, Kunyun; Zhang, Jianbo; Tang, Jie [Journal of Carbohydrate Chemistry, 2014, vol. 33, # 6, p. 313 - 325]
[4]Buttar, Simran; Caine, Julia; Goné, Evelyne; Harris, Reneé; Gillman, Jennifer; Atienza, Roxanne; Gupta, Ritu; Sogi, Kimberly M.; Jain, Lauren; Abascal, Nadia C.; Levine, Yetta; Repka, Lindsay M.; Rojas, Christian M. [Journal of Organic Chemistry, 2018, vol. 83, # 15, p. 8054 - 8080]
[5]Wittman, Mark D.; Halcomb, Randall L.; Danishefsky, Samuel J.; Golik, Jerzy; Vyas, Dolatrai [Journal of Organic Chemistry, 1990, vol. 55, # 7, p. 1979 - 1981]

10
[ 107-18-6 ]
[ 4098-06-0 ]
[ 135824-47-4 ]
[ 135824-46-3 ]

Yield	Reaction Conditions	Operation in experiment
	With 4 A molecular sieve; acetonitrile treated sulfonic acid resin; lithium bromide In acetonitrile for 0.5h; Ambient temperature; Yield given. Yields of byproduct given;
	With polymer-supported triphenylphosphine hydrobromide complex In dichloromethane at 20℃; for 16h; Inert atmosphere; optical yield given as %de;	4.13. Allyl 2-deoxy-3,4,6-tri-O-acetyl-d-galactopyranoside (13) Under argon, to a solution of 3,4,6-tri-O-acetyl d-galactal (1.0 g, 3.7 mmol, 1 equiv) 12 and allyl alcohol (816 μL, 12 mmol, 3.2 equiv) in anhydrous dichloromethane (20 mL) was added polymer-supported TPHB (PPh3·HBr)20 (240 mg, 0.74 mmol, 0.2 equiv). The mixture was stirred overnight, filtered, and concentrated in vacuo to provide the title compound (1.06g, 87%, pale yellow oil) as an α/β (4:1) mixture of anomers, in agreement with the litterature.21It is also possible to perform the reaction using nonsupported TPHB following the procedure described by Falk, Mioskowski et al.8 followed by purification by flash column chromatography (silica gel, 20% EtOAc in cyclohexane). 1H NMR (CDCl3, 300 MHz) (major isomer α) δ 5.97-5.84 (m, 1H), 5.37-5.17 (m, 4H), 5.06 (br d, J=2.9 Hz, 1H), 4.19-4.08 (m, 4H), 3.99 (ddt, J=12.9, 6.0, 1.3 Hz, 1H), 2.14 (s, 3H), 2.11 (m, 1H), 2.06 (s, 3H), 1.98 (s, 3H), 1.91 (m, 1H). 13C NMR (major isomer α) (CDCl3, 75 MHz) δ 170.5, 170.3, 170.0, 133.7, 117.5, 96.6, 68.2, 66.7, 66.6, 66.2, 62.4, 30.1, 20.8, 20.8 (2C). LRMS calcd for C15H22NaO8 [M+Na] 353.12, found 353.0.
71.429 % de	With Zr⁽⁴⁺⁾1.2CH₃O₃P^(2-)0.8C₆H₅O₆PS^(2-); lithium bromide In acetonitrile at 20 - 40℃; for 2h; Inert atmosphere; Overall yield = 95 %; regioselective reaction;

77.778 % de

With trimethylsilyl bromide; Triphenylphosphine oxide In neat (no solvent) at 20℃; Inert atmosphere; Green chemistry; Overall yield = 90 %; diastereoselective reaction;

General procedure for preparation of 2-deoxy-D-glycopyranosides. General procedure: Glycals (50.0mg, 1.0 equiv), acceptors (12-24, 2.0 equiv), and triphenylphosphine oxide (TPPO, 1.0 equiv) were mixed in a flame dried flask. After the reagents became homogeneous, TMSBr (1.0 equiv) was slowly added at room temperature under ambient atmosphere. After stirring for 1 to 2 hours, the mixture was directly purified by flash column chromatography on silica gel and then volatiles were removed in vacuo to affordexpected products. The products and yields are shown in Tables 2-4.

Reference： [1]Sabesan, Subramaniam; Neira, Susana [Journal of Organic Chemistry, 1991, vol. 56, # 18, p. 5468 - 5472]
[2]Location in patent: experimental part Donnard, Morgan; Tschamber, Théophile; Le Nouën, Didier; Desrat, Sandy; Hinsinger, Karen; Eustache, Jacques [Tetrahedron, 2011, vol. 67, # 2, p. 339 - 357]
[3]Rosati, Ornelio; Curini, Massimo; Messina, Federica; Marcotullio, Maria Carla; Cravotto, Giancarlo [Catalysis Letters, 2013, vol. 143, # 2, p. 169 - 175]
[4]Hsu, Mei-Yuan; Liu, Yi-Pei; Lam, Sarah; Lin, Su-Ching; Wang, Cheng-Chung [Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 1758 - 1764]

11
[ 107-18-6 ]
[ 4098-06-0 ]
[ 156616-68-1 ]

Yield	Reaction Conditions	Operation in experiment
87%	With carbon immobilized iron (III) chloride hexahydrate In dichloromethane at 20℃; for 4h; stereoselective reaction;	General Experimental Procedure for the Synthesis of2,3-Unsaturated Galactosides General procedure: To a stirred solution of tri-O-acetyl-D-galactal (50 mg, 0.185 mmol) in DCM(1 mL) were added the corresponding alcohol (0.204 mmol, 1.1 equiv) andFeCl3·6H2O/C (50 mol%) at ambient temperature. After the reaction was completed(monitored by TLC), the reaction mixture was filtered and the catalystwas washed with dichloromethane. After evaporation of the solvent under vacuum,the crude products were purified by silica gel column chromatography(petroleum ether/EtOAc = 10/1).
78%	With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 50℃; for 3h; Inert atmosphere; stereoselective reaction;
76%	With gold(III) chloride; phenylacetylene In dichloromethane at 35 - 37℃; for 5h; diastereoselective reaction;

75%	With indium(III) chloride In acetonitrile for 0.0152778h; microwave irradiation;
75%	With fluoroboronic acid adsorbed on silica gel In acetonitrile at 40℃; optical yield given as %de; stereoselective reaction;
68%	In chlorobenzene for 0.166667h; microwave irradiation;
52%	With boron trifluoride diethyl etherate In acetonitrile

Reference： [1]Zhou, Jiafen; Chen, Heshan; Shan, Junjie; Li, Juan; Yang, Guofang; Chen, Xuan; Xin, Kunyun; Zhang, Jianbo; Tang, Jie [Journal of Carbohydrate Chemistry, 2014, vol. 33, # 6, p. 313 - 325]
[2]Gurawa, Aakanksha; Kashyap, Sudhir; Kumar, Manoj; Reddy, Thurpu Raghavender [Organic and biomolecular chemistry, 2020, vol. 18, # 25, p. 4848 - 4862]
[3]Roy, Rashmi; Rajasekaran, Parasuraman; Mallick, Asadulla; Vankar, Yashwant D. [European Journal of Organic Chemistry, 2014, vol. 2014, # 25, p. 5564 - 5573]
[4]Das, Saibal Kumar; Reddy, K. Anantha; Roy, Joyita [Synlett, 2003, # 11, p. 1607 - 1610]
[5]Location in patent: scheme or table Rodríguez, Oscar Mariano; Colinas, Pedro Alfonso; Bravo, Rodolfo Daniel [Synlett, 2009, # 7, p. 1154 - 1156]
[6]Shanmugasundaram, Bhagavathy; Bose, Ajay K.; Balasubramanian, Kalpattu K. [Tetrahedron Letters, 2002, vol. 43, # 38, p. 6795 - 6798]
[7]Lesueur, Catherine; Nouguier, Robert; Bertrand, Michele Paula; Hoffmann, Pascale; De Mesmaeker, Alain [Tetrahedron, 1994, vol. 50, # 18, p. 5369 - 5380]

12
[ 100-49-2 ]
[ 4098-06-0 ]
cyclohexylmethyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-threoes-2-enopyranoside [ No CAS ]
Acetic acid (2R,3R,4R)-4-acetoxy-2-acetoxymethyl-6-cyclohexylmethoxy-tetrahydro-pyran-3-yl ester [ No CAS ]

Reference： [1]Journal of the Chemical Society. Chemical communications,1993,p. 704 - 706

13
[ 762-72-1 ]
[ 4098-06-0 ]
[ 129230-32-6 ]

Yield	Reaction Conditions	Operation in experiment
97%	With boron trifluoride diethyl etherate In acetonitrile at -50℃;
96%	With gold(III) chloride; phenylacetylene In dichloromethane at 35 - 37℃; for 3h; diastereoselective reaction;
94%	With ruthenium trichloride In acetonitrile at 20℃; for 0.166667h; Inert atmosphere;	4.2. General procedure for the RuCl3-catalyzed C-glycosylation General procedure: To a stirred solution of glycal (1 equiv) and acceptor or carbon nucleophile (1.2 equiv) in anhydrous acetonitrile (2 mL/mmol) under an atmosphere of argon was added RuCl3 (5 mol %) at room temperature. The reaction mixture was stirred until the complete consumption of the starting material (glycal). The solvent wasconcentrated in vacuo, the crude residue was re-dissolved in dichloromethane and loaded on a silica gel column. The product was purified by silica gel chromatography using Hexane/EtOAc to afford the 2,3-unsaturated-C-glycosides in excellent yields. All theproducts were confirmed by IR, 1H NMR, 13C NMR and MS/HRMS spectroscopy, and overall spectroscopic data were in complete agreement with assigned structures and also compared with literature data.

90%	With phosphomolybdic acid; silica gel In acetonitrile at 20℃; for 0.25h;
85%	With In(OSO₂CF₃)3; 4 A molecular sieve In dichloromethane at 27 - 32℃; for 5h;
80%	With erbium(III) triflate In dichloromethane at 20℃; for 36h;
78%	With indium(III) chloride In dichloromethane at 20 - 30℃; for 24h;
76%	With 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetonitrile at 70℃; for 48h;
76%	With gold(III) chloride In dichloromethane at 20℃; for 27h;
75%	With ammonium cerium (IV) nitrate In acetonitrile at 20℃; for 3h; Inert atmosphere; stereoselective reaction;	General procedure for Ferrier rearrangement of glycals by using CAN General procedure: A glycal (0.368 mmol) was dissolved in freshly dried CH3CN (3 mL) under N2 atmosphere. To this solution was added a nucleophile (0.736 mmol), followed by ceric ammonium nitrate (202 mg, 0.368 mmol). The reaction mixture was stirred at room temperature for the time indicated. After complete consumption of glycal (TLC monitoring), the reaction mixture was poured into a saturated NaHCO3 solution (5 mL), and extracted with ethyl acetate (3 × 5 mL). Combined organic extracts were washed with brine (1 × 10 mL), dried over Na2SO4, and concentrated under vacuum. The obtained residue was purified by column chromatography.
19%	With trimethylsilyl trifluoromethanesulfonate In dichloromethane; acetonitrile at -78℃; for 1h;

Reference： [1]Hanna, Issam; Lallemand, Jean-Yves; Wlodyka, Philippe [Tetrahedron Letters, 1994, vol. 35, # 36, p. 6685 - 6688] Hanna, Issam; Wlodyka, Philippe [Journal of Organic Chemistry, 1997, vol. 62, # 20, p. 6985 - 6990]
[2]Roy, Rashmi; Rajasekaran, Parasuraman; Mallick, Asadulla; Vankar, Yashwant D. [European Journal of Organic Chemistry, 2014, vol. 2014, # 25, p. 5564 - 5573]
[3]Srinivas, Batthula; Reddy, Thurpu Raghavender; Kashyap, Sudhir [Carbohydrate Research, 2015, vol. 406, p. 86 - 92]
[4]Yadav; Satyanarayana; Balanarsaiah; Raghavendra [Tetrahedron Letters, 2006, vol. 47, # 34, p. 6095 - 6098]
[5]Ghosh, Rina; Chakraborty, Arijit; Maiti, Dilip K. [Synthetic Communications, 2003, vol. 33, # 10, p. 1623 - 1632]
[6]Procopio, Antonio; Dalpozzo, Renato; De Nino, Antonio; Nardi, Monica; Russo, Beatrice; Tagarelli, Antonio [Synthesis, 2006, # 2, p. 332 - 338]
[7]Ghosh, Rina; De, Debasish; Shown, Biswajit; Maiti, Swaraj B. [Carbohydrate Research, 1999, vol. 321, # 1-2, p. 1 - 3]
[8]Toshima, Kazunobu; Ishizuka, Toru; Matsuo, Goh; Nakata, Masaya [Chemistry Letters, 1993, # 12, p. 2013 - 2016]
[9]Location in patent: experimental part Balamurugan, Rengarajan; Koppolu, Srinivasa Rao [Tetrahedron, 2009, vol. 65, # 39, p. 8139 - 8142]
[10]Ansari, Alafia A.; Reddy, Y. Suman; Vankar, Yashwant D. [Beilstein Journal of Organic Chemistry, 2014, vol. 10, p. 300 - 306]
[11]Toshima, Kazunobu; Ishizuka, Toru; Matsuo, Goh; Nakata, Masaya [Tetrahedron Letters, 1994, vol. 35, # 31, p. 5673 - 5676] Toshima, Kazunobu; Matsuo, Goh; Ishizuka, Toru; Ushiki, Yasunobu; Nakata, Masaya; Matsumura, Shuichi [Journal of Organic Chemistry, 1998, vol. 63, # 7, p. 2307 - 2313]

14
[ 4098-06-0 ]
[ 67817-41-8 ]

Yield	Reaction Conditions	Operation in experiment
94%	With Caswell No_. 744A; iron(III) trichloride hexahydrate; dihydrogen peroxide
77%	With ferric(III) chloride; Caswell No_. 744A; dihydrogen peroxide In lithium hydroxide monohydrate; acetonitrile at -30℃; for 3.5h; Inert atmosphere;	O-(2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-α-d-galactopyranosyl)-N-(9-fuorenylmethoxycarbonyl)-l-serine tert-butyl ester (16a) To a two-neck round-bottom flask containing iron trichloride (3.30g, 20.00mml) and sodium azide (0.86g, 13.35mmol) was added a solution of the galcal 11 (1.82g, 6.67mmol) in acetonitrile (56mL) at-30°C, followed by dropwise addition of 35% hydrogen peroxide (2.63mL, 30.03mmol) at the same temperature. The reaction mixture was stirred at the same temperature for 3.5h. After TLC analysis indicated that the starting material was consumed completed, the reaction mixture was allowed to warm to room temperature. The mixture was concentrated to give a residue, and diluted with DCM (250mL). The ether solution was washed with water (50mL×4), saturated NaHCO3 (50mL×3), brine (50mL×2), dried over MgSO4, filtered, and concentrated to give a crude residue, which was purified by column chromatography to give the glycosyl chloride 12 (1.792g, 77%), as a yellow oil.
	With oxalyl dichloride 2.) CH₂Cl₂, DMF, 1h, 0 deg C; Yield given. Multistep reaction;

78 %Spectr.	With Caswell No_. 744A; iron(III) trichloride hexahydrate; dihydrogen peroxide In lithium hydroxide monohydrate; acetonitrile at -30℃; for 3h;
	With Caswell No_. 744A; iron(III) trichloride hexahydrate; dihydrogen peroxide In acetonitrile at -30℃;	Azidochlorination of Glycals To a solution of the 3,4,6-tri-O-acetyl-D-galactal (1.0eq.) in acetonitrile, p. a. (80 mL, 8mL mmol-1) at -30 °C, ferric chloride hexahydrate (0.8eq.), sodium azide (1.1eq.) and hydrogen peroxide (1.1eq.; 33 % aq. solution) were added. The reaction was stirred in this temperature overnight. Then the mixture was diluted with diethyl ether and washed with water, sat. NaHCO3 and NaCl until the organic layer was decolorized. The organic layer was dried over MgSO4 and the solvent was evaporated. To avoid the loss of 3,4,6-tri-O-acetyl-2-azido-2-desoxy-α-D-galactopyranosyl chloride the chromatographic purification has been omitted.
	With Caswell No_. 744A; iron(III) trichloride hexahydrate; dihydrogen peroxide In acetonitrile at -20 - 10℃; for 2h;

Reference： [1]Singh, Yashonandini; Rodriguez Benavente, Maria C.; Al-Huniti, Mohammed H.; Beckwith, Donella; Ayyalasomayajula, Ramya; Patino, Eric; Miranda, William S.; Wade, Alex; Cudic, Maré [Journal of Organic Chemistry, 2020, vol. 85, # 3, p. 1434 - 1445]
[2]Liu, Si-Xian; Tsai, Yun-Tzu; Lin, Yu-Tung; Li, Jia-Yue; Chang, Che-Chien [Tetrahedron, 2019, vol. 75, # 52]
[3]Szweda, R.; Spohr, U.; Lemieux, R. U.; Schindler, D.; Bishop, D. F.; Desnick, R. J. [Canadian Journal of Chemistry, 1989, vol. 67, p. 1388 - 1391]
[4]Plattner, Carolin; Hoefener, Michael; Sewald, Norbert [Organic Letters, 2011, vol. 13, # 4, p. 545 - 547]
[5]Urbańczyk, Małgorzata; Jewgiński, Michał; Krzciuk-Gula, Joanna; Góra, Jerzy; Latajka, Rafał; Sewald, Norbert [Beilstein Journal of Organic Chemistry, 2019, vol. 15, p. 1581 - 1591]
[6]Njeri, Dancan K.; Ragains, Justin R. [Organic Letters, 2022]

15
[ 4098-06-0 ]
[ 196398-25-1 ]

Yield	Reaction Conditions	Operation in experiment
79%	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile at -10 - 20℃; for 12h; Inert atmosphere;	Compound 2 (12,0 g, 44 nnnol) was dissolved is acetonitrile (250 tsL) and cooled to -10°. In a separate nitrogen-flushed flask at -10°, NaN:; (4 3 g, 66 mol) and eerie ammonium nitrate (87.0 g, 158 mmol) were mixed and stirred vigorously. The solution of compound 2 in acetonitrile was added dropwise vi cannula, and the mixture allowed to slowly reach room temperature. The reaction mixture was allowed to stir for a total of 12 hours before dilution with ethyl acetate (500 L) and washing with water (3x) and brine (1 x). The organic layer was dried over sodium sulfate, evaporated, and purified on silica (20 50% EtOAc in Hexanes) to give compound 3 in 79% yield (13 J g, 34,9 mol). SH NMR (400 MHz, Chloroform-*/) 6.31 (d,/“ 4 1 Hz, 1H), 5 60 (d, ,/ = 8.8 Hz, 1 H), 5 43 (dd, J = 3.4, 1.3 Hz, 1H), 5.32 (t, J = 3.3 Hz, 1 H), 5.16 (dt /= 1 1.6, 3.4 Hz, 1 H), 4.96 (dd, J - 10 6, 3 3 Hz, i H), 4 39 - 4 28 (m, 1H), 4.14 - 4.00 (m, 5H), 3 76 (ddd, ,/- 13.5, 9.6, 4.7 Hz, 1 H), 2.19 - 2.05 (m, 6H), 2.05 - 1.S8 (m, 12H). C NMR (101 MHz, cdcl3) d 170.15-169.06, 97.91 , 97.79, 96.91 , 71.68, 71.45, 69.35, 68.42, 66.98, 66.53, 65.85, 64 75, 61.07, 60 84, 57.38, 55.82, 55.08, 20.31-20 20. HRMS: \| expected 399.076. found 399.073
79%	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile at -10 - 20℃; for 12h; Inert atmosphere;	8 Compound 2 (12.0 g, 44 mmol) was dissolved in acetonitrile (250 mL) and cooled to -10°. In a separate nitrogen-flushed flask at -10°, NaN3 (4.3 g, 66 mmol) and ceric ammonium nitrate (87.0 g, 158 mmol) were mixed and stirred vigorously. The solution of compound 2 in acetonitrile was added dropwise via cannula, and the mixture allowed to slowly reach room temperature. The reaction mixture was allowed to stir for a total of 12 hours before dilution with ethyl acetate (500 mL) and washing with water (3x) and brine (lx). The organic layer was dried over sodium sulfate, evaporated, and purified on silica (20-50% EtOAc in Hexanes) to give compound 3 in 79% yield (13. lg, 34.9 mmol). lH NMR (400 MHz, Chloroform-i/) d 6.31 (d,J = 4.1 Hz, 1H), 5.60 (d,J=8.8Hz, 1H), 5.43 (dd, J= 3.4, 1.3 Hz, 1 H), 5.32 (t, J= 3.3 Hz, 1H), 5.16 (dt, J= 11.6, 3.4 Hz, 1H),4.96 (dd, J = 10.6,3.3 Hz, I H), 4.39 -4.28 (m, 1H), 4.14 -4.00 (m, 5H), 3.76 (ddd,T= 13.5,9.6,4.7 Hz, 1H), 2.19-2.05 (m, 6H), 2.05 - 1.88 (m, 12H). (0711) 13C NMR (101 MHz, cdct3) d 170.15-169.06, 97.91, 97.79, 96.91, 71.68, 71.45, 69.35, 68.42, 66.98, 66.53, 65.85, 64.75, 61.07, 60.84, 57.38, 55.82, 55.08, 20.31-20.20. expected 399.076, found 399.073
77%	With Caswell No_. 744A; CAN In acetonitrile at -15℃;

65%	With Caswell No_. 744A; CAN In acetonitrile
60%	With Caswell No_. 744A; CAN; 4 A molecular sieve In acetonitrile at -15℃; for 3h;
51%	With Caswell No_. 744A; CAN In acetonitrile at -20 - -15℃; for 6h;
45%	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile at 20℃; for 12h;	2.2-62.1 Step 1: NaNs (4.3 g, 66 mmol) and CAN (87 g, 158 mmol) were added to a nitrogen- flushed flask, and the mixture were stirred vigorously at -10°C. Then a solution of (2R,3R,4R)-2- (acetoxymethyl)-3,4-dihydro-2H-pyran-3,4-diyl diacetate (A90-1, 12 g, 44 mmol) in MeCN (250 ml,) were added dropwise to the above mixture. The mixture was stirred at rt for 12 h. Then the reaction mixture was diluted with 500 mL EA. The organic phase was washed with () (400mL x 3) and brine, filtered and concentrated to give a yellow oil, which was purified by column chromatography to give (2R,3R,4R,5R)~2-(acetoxymethyi)-5-azido~6-(nitrooxy)tetrahydro-2H- pyran-3,4-diyl di acetate (A90-2, 7.5 g, 45% yield) as white solid. LC-MS (ESI) found: 377 j YM i G
45%	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile at -10 - 20℃; for 12h; Inert atmosphere;	5.5-62.1 Step 1: NaNs (4.3 g,66 mmol) and CAN (87 g,158 mmol) were added to a nitrogenflushed flask, and the mixture were stirred vigorously at -10°C. Then a solution of (2R,3R,4R)-2-(acetoxymethyl)-3,4-dihydro-2H-pyran-3,4-diyl diacetate (A90-1,12 g, 44 mmol) in MeCN (250 mL) were added dropwise to the above mixture. The mixture was stirred at rt for 12 h. Then the reaction mixture was diluted with 500 mL EA. The organic phase was washed with H2O (400mL x 3) and brine, filtered and concentrated to give a yellow oil, which was purified by column chromatography to give (2R,3R,4R,5R)-2-(acetoxymethyl)-5-azido-6-(nitrooxy)tetrahydro-2H- pyran-3,4-diyl diacetate (A90-2, 7.5 g, 45% yield) as white solid. LC-MS (ESI) found: 377 [M+H]+.
45%	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile at -10 - 20℃; for 12h; Inert atmosphere;	5.5-62.1 Step 1: NaNs (4.3 g,66 mmol) and CAN (87 g,158 mmol) were added to a nitrogenflushed flask, and the mixture were stirred vigorously at -10°C. Then a solution of (2R,3R,4R)-2-(acetoxymethyl)-3,4-dihydro-2H-pyran-3,4-diyl diacetate (A90-1,12 g, 44 mmol) in MeCN (250 mL) were added dropwise to the above mixture. The mixture was stirred at rt for 12 h. Then the reaction mixture was diluted with 500 mL EA. The organic phase was washed with H2O (400mL x 3) and brine, filtered and concentrated to give a yellow oil, which was purified by column chromatography to give (2R,3R,4R,5R)-2-(acetoxymethyl)-5-azido-6-(nitrooxy)tetrahydro-2H- pyran-3,4-diyl diacetate (A90-2, 7.5 g, 45% yield) as white solid. LC-MS (ESI) found: 377 [M+H]+.
42%	With Caswell No_. 744A; ammonium cerium (IV) nitrate
40%	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile
35%	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile
	With Caswell No_. 744A; CAN In acetonitrile at -25℃; for 20h; Yield given;
	With Caswell No_. 744A; CAN In acetonitrile at -25℃; for 3h;
	With cerium (IV) ammonium nitrate In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; acetonitrile	27 7.27. To a solution of tri-O-acetyl-D-galactal 67 (25.0 g, 91.8 mmol) in 1000 mL of distilled CH3 CN at -20° C. is added sodium azide (8.96 g, 138 mmol), followed by ceric ammonium nitrate (151 g, 276 mmol). The reaction suspension is stirred vigorously at -15 to -20° C. for 24 h and then filtered through Celite. The filtrate is diluted with 1000 mL of ice water and extracted with CH2 Cl2 (3*200 mL). The combined organic layers are dried over Na2 SO4, concentrated, and purified by flash chromatography (10% EtOAc/hexane) to give 17.5 g (51%) of 2-azido-2-deoxy-1-O-nitro-3,4,6-tri-O-acetyl-α,β-D-galactopyranose 68 as a mixture of anomers: Rf 0.26 (25% EtOAc/hexane); 1 H NMR (CDCl3, 270 MHz, mixture of anomers) δ 6.32 (d, J=4.0 Hz, 1 H, H-1α), 5.55 (d, J=8.9 Hz, 1 H, H-1β), 5.48 (d, J=3.0 Hz, 1 H, H-4α), 5.37 (d, J=3.0 Hz, 1 H, H-4β), 5.23 (dd, J=11.6, 3.3 Hz, 1 H, H-3α), 4.93 (dd, J=10.6, 3.3 Hz, 1 H, H-3β), 4.35 (t, J=6.6 Hz, 1 H, H-5α), 3.9-4.2 (m, 6 H, H-2α, H-5β, H-6β, H-6α), 3.81 (dd, J=10.6, 8.9 Hz, 1 H, H-2β), 1.95-2.25 (6s,18 H).
	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile at -20℃;
	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile at -20℃;
	With Caswell No_. 744A; ammonium cerium (IV) nitrate In acetonitrile at -15℃; for 5h; Inert atmosphere;

Reference： [1]Current Patent Assignee: YALE UNIVERSITY - WO2019/199621, 2019, A1 Location in patent: Page/Page column 86-87
[2]Current Patent Assignee: YALE UNIVERSITY - WO2019/199634, 2019, A1 Location in patent: Page/Page column 70; 92
[3]Renaudet, Olivier; Dumy, Pascal [Tetrahedron Letters, 2004, vol. 45, # 1, p. 65 - 68]
[4]Svarovsky, Serge A.; Barchi Jr., Joseph J. [Carbohydrate Research, 2003, vol. 338, # 19, p. 1925 - 1935]
[5]Mitchell; Pratt; Hruby; Polt [Journal of Organic Chemistry, 2001, vol. 66, # 7, p. 2327 - 2342]
[6]Bukowski, Ralph; Morris, Laura M.; Woods, Robert J.; Weimar, Thomas [European Journal of Organic Chemistry, 2001, # 14, p. 2697 - 2705]
[7]Current Patent Assignee: AVILAR THERAPEUTICS - WO2021/155317, 2021, A1 Location in patent: Page/Page column 372; 400
[8]Current Patent Assignee: AVILAR THERAPEUTICS - WO2022/35997, 2022, A1 Location in patent: Page/Page column 237; 267-268
[9]Current Patent Assignee: AVILAR THERAPEUTICS - WO2022/35997, 2022, A1 Location in patent: Page/Page column 237; 267-268
[10]Location in patent: scheme or table Cai, Hui; Huang, Zhi-Hua; Shi, Lei; Zou, Peng; Zhao, Yu-Fen; Kunz, Horst; Li, Yan-Mei [European Journal of Organic Chemistry, 2011, # 20-21, p. 3685 - 3689]
[11]Location in patent: scheme or table Balcerzak, Anna K.; Ferreira, Sandra S.; Trant, John F.; Ben, Robert N. [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 4, p. 1719 - 1721]
[12]Location in patent: scheme or table Heggemann, Carolin; Budke, Carsten; Schomburg, Benjamin; Majer, Zsuzsa; Wibrock, Marco; Koop, Thomas; Sewald, Norbert [Amino Acids, 2010, vol. 38, # 1, p. 213 - 222]
[13]Broddefalk, Johan; Nilsson, Ulf; Kihlberg, Jan [Journal of Carbohydrate Chemistry, 1994, vol. 13, # 1, p. 129 - 132]
[14]Bay, Sylvie; Huteau, Valérie; Zarantonelli, Maria-Leticia; Pires, René; Ughetto-Monfrin, Joël; Taha, Muhamed-Kheir; England, Patrick; Lafaye, Pierre [Journal of Medicinal Chemistry, 2004, vol. 47, # 16, p. 3916 - 3919]
[15]Current Patent Assignee: GOVERNMENT OF THE UNITED STATES; NEIMAN SA - US6040433, 2000, A
[16]Current Patent Assignee: YALE UNIVERSITY - WO2021/72269, 2021, A1 Location in patent: Page/Page column 157
[17]Current Patent Assignee: YALE UNIVERSITY - WO2021/72246, 2021, A1 Location in patent: Page/Page column 3; 77
[18]Chapa-Villarreal, Fabiola A.; Chiaramonte, Jonathan; Piazza, Sabrina M.; Reynolds, Michael R.; Trant, John F.; Xu, Peihan [New Journal of Chemistry, 2021, vol. 45, # 41, p. 19224 - 19227]

16
[ 4098-06-0 ]
[ 21193-75-9 ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium methoxide In methanol
99%	With lipase A from Aspergillus niger In aq. phosphate buffer; acetonitrile at 25℃; for 1h; Enzymatic reaction;
99%	With methanol; sodium methoxide at 20℃; for 0.5h;	3.1. General Procedure for the Synthesis of Glycals General procedure: A catalytic amount of MeONa (0.03 g, 0.57 mmol) was added to a solution of tri-O-acetyl-D-glycal (2.5 g, 9.18 mmol) in methanol (25 mL) and the resulting reaction mixture was stirred at rt. The progress of reactions was monitored by silica gel thin-layer chromatography plates. After 30 min, the solution was filtered on a Schott funnel over a resin layer (Amberlite IR120) and celite. Evaporation of the organic solvent afforded a pure product.

97%	With ammonia In methanol at 20℃; for 5h;
97.6%	With methanol; potassium carbonate
96%	With methanol; potassium permanganate; trimethyl-sulfonium iodide at 25℃; chemoselective reaction;
95%	With methanol; sodium methoxide at 20℃; Inert atmosphere;
95%	Stage #1: (2R,3R,4R)-2-(acetoxymethyl)-3,4-dihydro-2H-pyran-3,4-diyl diacetate With sodium methoxide In methanol at 25℃; for 2h; Inert atmosphere; Stage #2:
93%	With sodium methoxide In methanol at 20℃; for 2h;	6.6-3.1 Step 1: To a solution of (2R,3R,4R)-2-(acetoxymethyl)-3,4-dihydro-2H-pyran-3,4-diyl diacetate (A126-1, 30.0 g, 55.1 mmol) in MeOH (300 mL) was added NaOMe (31.0 mL,165.3 mmol, 5.4 M in MeOH) at room temperature. The mixture was stirred at room temperature for 2 hours. The reaction was neutralized by the addition of Amberlite IR 120 (H+) ion exchange resin. The solution was filtered through a glass fritted funnel with a pad of Celite to remove the resin. The filtrate was concentrated to dryness to give a crude triol. The crude material was passed through a plug of silica (70:30 to 85: 15 EtOAc/hexanes) to give D-galactal triol (A126-2,15.0 g 93%) as white solid. LC-MS (ESI) found: 147 [M+H]+.
93%	With sodium methoxide In methanol at 20℃; for 2h;	6.6-3.1 Step 1: To a solution of (2R,3R,4R)-2-(acetoxymethyl)-3,4-dihydro-2H-pyran-3,4-diyl diacetate (A126-1, 30.0 g, 55.1 mmol) in MeOH (300 mL) was added NaOMe (31.0 mL,165.3 mmol, 5.4 M in MeOH) at room temperature. The mixture was stirred at room temperature for 2 hours. The reaction was neutralized by the addition of Amberlite IR 120 (H+) ion exchange resin. The solution was filtered through a glass fritted funnel with a pad of Celite to remove the resin. The filtrate was concentrated to dryness to give a crude triol. The crude material was passed through a plug of silica (70:30 to 85: 15 EtOAc/hexanes) to give D-galactal triol (A126-2,15.0 g 93%) as white solid. LC-MS (ESI) found: 147 [M+H]+.
92%	With triethylamine In methanol; lithium hydroxide monohydrate at 20℃; for 24h;
92%	With lithium hydroxide monohydrate; triethylamine In methanol at 20℃;
89%	With methanol; natrium
87%	With sodium methoxide In methanol for 72h;
	With ammonia In methanol for 15h; Ambient temperature; Yield given;
	With sodium methoxide In methanol
	With natrium In methanol for 12h;
	With anion-exchange resin (Amberlite IRN-78, OH^- form) In methanol for 15h; Ambient temperature;
	With ammonia In methanol
0.73 g	With sodium methoxide In methanol at 20℃; for 24h;
	With sodium methoxide In methanol
	With methanol; sodium methoxide at 20℃; for 3h;
	With sodium methoxide In methanol at 20℃;
	With sodium methoxide In methanol at 20℃; for 1.5h;
	With sodium methoxide In methanol
	With methanol; sodium methoxide at 20℃; for 2h;
	With sodium methoxide In methanol at 20℃;
	With sodium methoxide In methanol at 20℃; for 24h; Inert atmosphere;
	With methanol; sodium methoxide at 0 - 20℃; for 1h; Inert atmosphere;
	With methanol; natrium at 20℃; for 0.166667h; Inert atmosphere;	D-Galactal Using a modification of Kozikowski’s procedure,1 a magnetically stirred solution of D-galactose (S2, 125 mg, 0.7 mmol) in acetic anhydride (75 mL, 790 mmol) was treated dropwise with conc. perchloric acid (0.45 mL, 6.9 mmol). The remaining D-galactose (19.9 g, 110.3 mmol) was slowly added over 30 minutes, at a rate that maintained a temperature of 40-50 °C. Upon complete addition of D-galactose, the solution was allowed to cool to room temperature, then treated with a 33% (w/w) solution of hydrobromic acid in acetic acid (75 mL, 410 mmol). After 90 minutes, the solution was diluted with dichloromethane (180 mL) and washed with ice-cold water (2 x 50 mL), then with cold saturated sodium bicarbonate solution (4 x 100 mL). The organic phase was dried, filtered and concentrated to afford crude tetra-O-acetyl-α-D-galactopyranosyl bromide as a pale-yellow oil.A mechanically stirred dispersion of zinc dust (48.0 g, 734 mmol) in water (150 mL) was cooled to 0 °C, diluted with acetic acid (150 mL), then treated dropwise over one hour with a solution of tetra-O-acetyl-α-D-galactopyranosyl bromide in diethyl ether (150 mL). The reaction was allowed to warm to room temperature and left to proceed overnight. The solution was filtered, then diluted with dichloromethane (200 mL). The solution was then washed successively with water (3 x 60 mL), saturated sodium bicarbonate solution (3 x 50 mL) and brine (60 mL). The organic phase was dried, filtered and concentrated to provide tri-O-acetyl-D-galactal (S5) (27.7 g) as a pale-yellow oil.A solution of triethylamine (110 mL, 780 mmol) in methanol (50% of an aqueous solution, 1100 mL) was treated with tri-O-acetyl-D-galactal (27.7 g) and stirred for 90 minutes. The mixture was concentrated to liberate crude D-galactal, contaminated with triethylamine. The crude mixture was successively treated with portions of methanol, then concentrated to remove the triethylamine. The oil was dissolved in methanol (15 mL), then diluted successively with acetone (100 mL) and diethyl ether (200 mL), which led to the precipitation of impurities. The solution was filtered and concentrated to afford D-galactal as a pale-brown solid (6.63 g, 41% crude yield), which was used without further purification.
	With potassium carbonate In methanol at 20℃; for 3h;
	With sodium methoxide In methanol at 0℃; for 3h;
	With methanol; sodium methoxide at 20℃; for 3h; Inert atmosphere;
2.7 g	With methanol; sodium methoxide at 20℃;	4 (4) The crude product compound c (5.5 g, 20.2 mmol) obtained in the previous step was placed in a round bottom flask (250 ml). Then, methanol (84.0 ml) was added thereto, and the mixture was stirred to dissolve, followed by the addition of sodium methoxide (0.55 g, 10.2 mmol), and reacted at room temperature for 1-2 h. The reaction is carried out under normal temperature conditions to remove the acetic acid group (Ac). The reaction is judged by thin layer chromatography (dichloromethane: methanol = 10:1). After the reaction is completed, acetic acid is added to adjust the pH to neutral or weakly alkaline, and the pressure is reduced. Distillation (-0.09 MPa, 45 ° C) to remove excess solvent and spin dry to obtain a crude product as a pale yellow syrup. Separation by silica gel column chromatography (dichloromethane: Methanol = 5:1) gave the important intermediate compound d (perhydroxy galactose) (2.7 g, 18.5 mmol), The yield was 77.1%.
	With sodium methoxide In methanol Inert atmosphere;
	With methanol; sodium methoxide at 20℃; for 1.5h; Inert atmosphere;
	With sodium methoxide In methanol at 0℃; for 3h;

Reference： [1]Czernecki, S.; Ayadi, E.; Randriamandimby, D. [Journal of Organic Chemistry, 1994, vol. 59, # 26, p. 8256 - 8260]
[2]Dunne, Anthony; Palomo, Jose M. [RSC Advances, 2016, vol. 6, # 92, p. 88974 - 88978]
[3]Leśniak, Stanisław; Malinowska, Martyna; Tracz, Aleksandra; Zawisza, Anna [Molecules, 2022, vol. 27, # 6]
[4]Mamidyala, Sreeman K.; Dutta, Sanjay; Chrunyk, Boris A.; Preville, Cathy; Wang, Hong; Withka, Jane M.; McColl, Alexander; Subashi, Timothy A.; Hawrylik, Steven J.; Griffor, Matthew C.; Kim, Sung; Pfefferkorn, Jeffrey A.; Price, David A.; Menhaji-Klotz, Elnaz; Mascitti, Vincent; Finn [Journal of the American Chemical Society, 2012, vol. 134, # 4, p. 1978 - 1981]
[5]Current Patent Assignee: JIANGXI NORMAL UNIVERSITY - CN113200951, 2021, A Location in patent: Paragraph 0056-0058
[6]Gurawa, Aakanksha; Kashyap, Sudhir; Kumar, Manoj [RSC Advances, 2021, vol. 11, # 31, p. 19310 - 19315]
[7]Vedachalam, Seenuvasan; Tan, Shi Min; Teo, Hui Ping; Cai, Shuting; Liu, Xue-Wei [Organic Letters, 2012, vol. 14, # 1, p. 174 - 177]
[8]Keith, D. Jamin; Townsend, Steven D. [Journal of the American Chemical Society, 2019, vol. 141, # 32, p. 12939 - 12945]
[9]Current Patent Assignee: AVILAR THERAPEUTICS - WO2022/35997, 2022, A1 Location in patent: Page/Page column 286-288
[10]Current Patent Assignee: AVILAR THERAPEUTICS - WO2022/35997, 2022, A1 Location in patent: Page/Page column 286-288
[11]Chatterjee, Nirbhik; Pandit, Palash; Halder, Samiran; Patra, Amarendra; Maiti, Dilip K. [Journal of Organic Chemistry, 2008, vol. 73, # 19, p. 7775 - 7778]
[12]Maiti, Dilip K.; Halder, Samiran; Pandit, Palash; Chatterjee, Nirbhik; De Joarder, Dripta; Pramanik, Nabyendu; Saima, Yasmin; Patra, Amarendra; Maiti, Prabir K. [Journal of Organic Chemistry, 2009, vol. 74, # 21, p. 8086 - 8097]
[13]Jacquinet [Carbohydrate research, 1990, vol. 199, # 2, p. 153 - 181]
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[15]Kozilowski; Lee [Journal of Organic Chemistry, 1990, vol. 55, # 3, p. 863 - 870]
[16]Bovin, Nicolai V.; Zurabyan, Sergei E.; Khorlin, Anatoly Y. [Carbohydrate Research, 1981, vol. 98, p. 25 - 36]
[17]Lafont, Dominique; Descotes, Gerard [Carbohydrate Research, 1987, vol. 166, p. 195 - 210]
[18]Czernecki, S.; Vijayakumaran, K.; Ville, G. [Journal of Organic Chemistry, 1986, vol. 51, # 26, p. 5472 - 5475]
[19]Kwon, Ohyun; Danishefsky, Samuel J. [Journal of the American Chemical Society, 1998, vol. 120, # 7, p. 1588 - 1599]
[20]Costantino, Valeria; Fattorusso, Ernesto; Imperatore, Concetta; Mangoni, Alfonso [Tetrahedron, 2002, vol. 58, # 2, p. 369 - 375]
[21]Cheshev; Kononov; Tsvetkov; Shashkov; Nifantiev [Russian Journal of Bioorganic Chemistry, 2002, vol. 28, # 5, p. 419 - 429]
[22]Aurrecoechea, José M.; Arrate, Mónica; Gil, Jesús H.; López, Beatriz [Tetrahedron, 2003, vol. 59, # 29, p. 5515 - 5522]
[23]Aurrecoechea, José M.; Gil, Jesús H.; López, Beatriz [Tetrahedron, 2003, vol. 59, # 36, p. 7111 - 7121]
[24]Dubbaka, Srinivas Reddy; Steunenberg, Peter; Vogel, Pierre [Synlett, 2004, # 7, p. 1235 - 1238]
[25]Postema, Maarten H. D.; Piper, Jared L.; Betts, Russell L.; Valeriote, Frederick A.; Pietraszkewicz, Halina [Journal of Organic Chemistry, 2005, vol. 70, # 3, p. 829 - 836]
[26]Pilgrim, Wayne; Murphy, Paul V. [Organic Letters, 2009, vol. 11, # 4, p. 939 - 942]
[27]Location in patent: experimental part Li, Hou-Hua; Ye, Xin-Shan [Organic and Biomolecular Chemistry, 2009, vol. 7, # 18, p. 3855 - 3861]
[28]Chabre, Yoann M.; Giguere, Denis; Blanchard, Bertrand; Rodrigue, Jacques; Rocheleau, Sylvain; Neault, Mathieu; Rauthu, Subhash; Papadopoulos, Alex; Arnold, Alexandre A.; Imberty, Anne; Roy, Rene [Chemistry - A European Journal, 2011, vol. 17, # 23, p. 6545 - 6562]
[29]Durantie, Estelle; Bucher, Christoph; Gilmour, Ryan [Chemistry - A European Journal, 2012, vol. 18, # 26, p. 8208 - 8215]
[30]Moore, Peter W.; Schuster, Julia K.; Hewitt, Russell J.; Stone, M. Rhia L.; Teesdale-Spittle, Paul H.; Harvey, Joanne E. [Tetrahedron, 2014, vol. 70, # 39, p. 7032 - 7043]
[31]Shu, Penghua; Zeng, Jing; Tao, Jinyi; Zhao, Yueqi; Yao, Guangmin; Wan, Qian [Green Chemistry, 2015, vol. 17, # 4, p. 2545 - 2551]
[32]Wang, Bang; Xiong, De-Cai; Ye, Xin-Shan [Organic Letters, 2015, vol. 17, # 22, p. 5698 - 5701]
[33]Mabit, Thibaud; Siard, Aymeric; Legros, Frédéric; Guillarme, Stéphane; Martel, Arnaud; Lebreton, Jacques; Carreaux, François; Dujardin, Gilles; Collet, Sylvain [Chemistry - A European Journal, 2018, vol. 24, # 53, p. 14069 - 14074]
[34]Current Patent Assignee: SICHUAN UNIVERSITY OF SCIENCE AND ENGINEERING - CN109912642, 2019, A Location in patent: Paragraph 0031-0032; 0037
[35]Ahadi, Somayeh; Awan, Shahid I.; Werz, Daniel B. [Chemistry - A European Journal, 2020]
[36]Conti, Gabriele; Cramer, Jonathan; Ernst, Beat; Girardi, Benedetta; Jiang, Xiaohua; Kokot, Maja; Kroezen, Blijke S.; Luisoni, Enrico; Müller, Jennifer; Rabbani, Said; Ricklin, Daniel; Schwardt, Oliver [ChemMedChem, 2020, vol. 15, # 18, p. 1706 - 1719]
[37]Yu, Changyue; Liu, Yichu; Xie, Xiong; Hu, Shulei; Zhang, Shurui; Zeng, Mingjie; Zhang, Dan; Wang, Jiang; Liu, Hong [Advanced Synthesis and Catalysis, 2021, vol. 363, # 21, p. 4926 - 4931]

17
[ 4098-06-0 ]
[ 166329-00-6 ]

Yield	Reaction Conditions	Operation in experiment
98%	With Oxone; sodium hydrogencarbonate In dichloromethane; water; acetone at 0 - 20℃; for 0.75h; Cooling with ice;	3.2. General procedure for the preparation of the 1,2-anhydrosugars 4 and 6 General procedure: The corresponding glycal 3 or 5 (1.00 mmol) was dissolved in an ice bath cooled biphasic solution of CH2Cl2 (4 mL), acetone (0.4 mL) and saturated aqueous NaHCO3 (6.5 mL). The mixture was vigorously stirred and a solution of Oxone (1.23 g, 2.00 mmol) in H2O (5 mL) was added dropwise over 15 min. The crude reaction was vigorously stirred at 0 °C for 30 min and then allowed to warm to room temperature until complete consumption of the glycal (TLCmonitoring). The organic phase was separated and the aqueous phase was extracted with CH2Cl2 (2 x 4 mL). The combined organic phases were dried over MgSO4, filtered and concentrated to afford the 1,2-anhydro-pyranoses 4 (90%, mixture D-gluco/D-manno 7:1) or 6 (98%, only α-epoxide). The crude could not be purified due the inherent instability of 1,2-anhydrosugars.
	With perfluoro(1-butyl-3-propyloxaziridine) for 0.0833333h; Ambient temperature; Yield given;
	With 3,3-dimethyldioxirane

With 3,3-dimethyldioxirane In dichloromethane; acetone

Reference： [1]Castilla, Javier; Rísquez, Rocío; Higaki, Katsumi; Nanba, Eiji; Ohno, Kousaku; Suzuki, Yoshiyuki; Díaz, Yolanda; Ortiz Mellet, Carmen; García Fernández, José M.; Castillón, Sergio [European Journal of Medicinal Chemistry, 2015, vol. 90, p. 258 - 266]
[2]Cavicchioli, Marcello; Mele, Andrea; Montanari, Vittorio; Resnati, Giuseppe [Journal of the Chemical Society. Chemical communications, 1995, # 8, p. 901 - 902]
[3]Chiara, Jose Luis; Sesmilo, Esther [Angewandte Chemie - International Edition, 2002, vol. 41, # 17, p. 3242 - 3246]
[4]Li, Yao; Tang, Pingping; Chen, Youxi; Yu, Biao [Journal of Organic Chemistry, 2008, vol. 73, # 11, p. 4323 - 4325]

18
[ 140681-55-6 ]
[ 4098-06-0 ]
1-(3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-α-D-galactopyranosyl)-4-chloromethyl-1,4-diazonia-bicyclo[2.2.2]octane bis(tetrafluoroborate) [ No CAS ]

Reference： [1]Tetrahedron,1998,vol. 54,p. 4839 - 4848

19
[ 2140-11-6 ]
[ 4098-06-0 ]
4'',6''-di-O-acetyl-2'',3''-dideoxy-α-D-threo-hex-2''-enopyranosyl-(1->5)-2',3'-O-isopropylideneinosine [ No CAS ]

Reference： [1]Tetrahedron Asymmetry,1999,vol. 10,p. 2119 - 2127

20
[ 140681-55-6 ]
[ 4064-06-6 ]
[ 4098-06-0 ]
ethanimidic acid, N-(2-fluoro-2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranosyl ester [ No CAS ]

Reference： [1]Journal of Organic Chemistry,1999,vol. 64,p. 5264 - 5279

21
[ 4098-06-0 ]
[ 136520-46-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With water In acetonitrile at 20℃; for 4 - 5h; phosphate buffer; Enzymatic reaction;	2; 6 Example 2; 3, 4-Di-O-acetyl-D-galactal; To a 20 mM solution of 3,4,6-tri-O-acetyl-D-galactal (commercial: Sigma- Aldrich) in 50 mM phosphate buffer containing 20% acetonitrile at a pH kept constant at a 4.0 value, 1 g of Candida Rugosa lipase immobilized on octyl-agarose gel as described in Preparation I of WO 03/057894 was added. The solution was let to stand under mechanical stirring at room temperature, by controlling its course by HPLC and keeping the pH of 4 constant by automatic titration. After a 5 -hour incubation, 90% conversion of the substrate was observed. The organic solvent was removed by evaporation under reduced pressure. The product was extracted from the aqueous solution with ethyl acetate. After evaporation of the collected organic extracts under reduced pressure, the residue was purified on a silica gel chromatographic column by using a H-hexane/ethyl acetate 4/6 (v/v) mixture as eluent. The 6-hydroxy derivative was isolated in pure form and characterized by COSY 2D NMR studies, in order to determine the correct position of the hydrolyzed acetyl group. Yield: 100%. 1H-NMR: in CDCl3 (δ=ppm): 6.40 (dd, J=6.2Hz, 1.6Hz; IH-I), 5.48 (m, J=UHz; 1H-4), 4.75 (m, J=2.4Hz; 1H-2), 4.15-4.30 (m, J5,6= 7.4Hz, J6j6.=12.2Hz; 3H-5/6a,b), 4.10-4.15 (m, J=4.7Hz; 1H-3), 2.11 (CH3, s, 3H), 2.03(CH3, s, 3H).; Example 6; 3, 6-Di-O-acetyl-D-galactal; By operating as described in Example 5, starting from a 20 mM solution of 3,4,6-tri- O-acetyl-D-galactal (commercial: Sigma-Aldrich) in 50 mM phosphate buffer containing 20% acetonitrile at a pH maintained constant at a value of 4 and from 1 g of Candida rugosa lipase, a 90% conversion to 3,4-di-O-acetyl-D-galactal was observed. After removal of the immobilized enzyme by filtration, the obtained solution was brought to 40C and, rapidly, to pH 9.5 by rapid addition of a NaOH solution, then it was treated as described in Example 2. Thus, 3,6-di-O-acetyl-D- galactal was obtained in a 70% global yield.1H-NMR: in CDCl3 (δ=ppm): 6.43 (dd, J=6.3, 1.2 Hz; IH-I), 5.37 (m, J=4.7 Hz IH- 3), 4.65 (ddd, J=3.8, 1.7 Hz, 1H-2), 4.30 (m, H-5), 4.15-4.32 (2 m, 2H-6A,B), 4.15 (m 1H-4), 2.41(bs, IH-OH) 2.08-2.06 (2s, 6H).
99%	With sodium acetate In water; acetonitrile for 24h; Enzymatic reaction;	9 2.3.9 3,4-Di-O-acetyl-d-galactal (9) Tri-O-acetyl-galactal (720mg, 2.64 mmol) was hydrolyzed in 100mL solution of sodium acetate (50mM) (80%) and acetonitrile (20%) at pH 5, using 3g of octyl-CRL immobilized preparation. After 24h, the substrate completely disappeared (checked by TLC and HPLC). The aqueous solution was filtrated and saturated with NaCl and then extracted with ethyl acetate (5× 50mL). The collected organic layers were dried over anhydrous Na2SO4, which was then removed by filtration and concentrated under vacuum. Then, diethyl ether was added and removed under vacuum to afford 9 as a white glassy solid (603mg, 99%). TLC of 9: CH2Cl2:CH3OH 9:1 v/v, Rf=0.67, HPLC (NH4H2PO4 10mM buffer:ACN 7:3 v/v, pH 4) Rt=5.2min. 1H NMR (500MHz, CDCl3) δ: 6.50 (dd, J=6.2, 1.8Hz, 1H, H-1), 5.60-5.55 (m, 1H, H-3), 5.50-5.44 (dt, J=7.4, 3.6Hz, 1H, H-4), 4.73 (dt, J=5.9, 2.8Hz, 1H, H-2), 4.22-4.16 (m, J=7Hz, 1H, H-5), 3.83-3.61 (dd, J=11.6, 5.8Hz, 2H, H-6A, H-6B), 2.31 (bs, 1H, OH), 2.16 (s, 3H, CH3), 2.05 (s, 3H, CH3).
90%	With immobilized lipase from Candida rugosa In phosphate buffer; acetonitrile at 25℃; for 5h;

65%

With phosphate buffer; pig liver esterase at 37℃; for 0.5h; Enzymatic reaction;

Reference： [1]Current Patent Assignee: INNOVATE BIOTECHNOLOGY; INNOVATIVE BIOTECHNOLOGY - WO2008/81270, 2008, A2 Location in patent: Page/Page column 8-9; 11
[2]Brabcova, Jana; Carrasco-Lopez, Cesar; Bavaro, Teodora; Hermoso, Juan A.; Palomo, Jose M. [Journal of Molecular Catalysis B: Enzymatic, 2014, vol. 107, p. 31 - 38]
[3]Filice, Marco; Palomo, Jose M.; Bonomi, Paolo; Bavaro, Teodora; Fernandez-Lafuente, Roberto; Guisan, Jose M.; Terreni, Marco [Tetrahedron, 2008, vol. 64, # 39, p. 9286 - 9292]
[4]Pfau, Roland; Kunz, Horst [Synlett, 1999, # 11, p. 1817 - 1819]

22
[ 100-51-6 ]
[ 4098-06-0 ]
benzyl 4,6-di-O-acetyl-2,3-didesoxy-α-D-threo-hex-2-enopyranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With carbon immobilized iron (III) chloride hexahydrate In dichloromethane at 20℃; for 0.666667h; stereoselective reaction;	General Experimental Procedure for the Synthesis of2,3-Unsaturated Galactosides General procedure: To a stirred solution of tri-O-acetyl-D-galactal (50 mg, 0.185 mmol) in DCM(1 mL) were added the corresponding alcohol (0.204 mmol, 1.1 equiv) andFeCl3·6H2O/C (50 mol%) at ambient temperature. After the reaction was completed(monitored by TLC), the reaction mixture was filtered and the catalystwas washed with dichloromethane. After evaporation of the solvent under vacuum,the crude products were purified by silica gel column chromatography(petroleum ether/EtOAc = 10/1).
87%	With 3,5-dinitrobenzoic acid In acetonitrile at 80℃; for 2h;	General procedure for preparation of 2,3-unsaturated glycosides General procedure: To a mixture of 2,4,6-tri-O-acetyl-D-glycal (135 mg, 0.5 mmol) and alcohol or thiol (1equiv) in acetonitrile (5 mL) was added 3,5-dinitrobenzoic acid (0.1 mmol, 20 mol%) at roomtemperature. The mixture was stirred at 80 oC for a specified period of time (Table 1), and theprogress of reaction was monitored by TLC analysis. Evaporation of the solvent under reducedpressure, followed by purification of the residue by silica gel column chromatography (ethylacetate/hexanes, 1/4, as the eluent) gave the desired 2,3-unsaturated glycoside.
86%	With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 50℃; for 1h; Inert atmosphere; stereoselective reaction;

85%	In chlorobenzene for 0.15h; microwave irradiation;
84%	With tris(pentafluorophenyl)borate In toluene at 75℃; for 1.5h; Sealed tube; stereoselective reaction;
82%	Stage #1: benzyl alcohol; triacetyl-D-galactal In dichloromethane for 4h; Reflux; Stage #2: With montmorillonite K₁₀ Clay In dichloromethane at 0 - 5℃; Heating;
76%	With perchloric acid; silica gel In acetonitrile at 20℃; for 1.33333h;
76%	With trimethylsilyl trifluoromethanesulfonate; 1-(n-butyl)-3-methylimidazolium triflate at 20℃; for 1.66667h; stereoselective reaction;
75%	With gold(III) chloride; phenylacetylene In dichloromethane at 35 - 37℃; for 3h; diastereoselective reaction;
74%	With fluoroboronic acid adsorbed on silica gel In acetonitrile at 40℃; optical yield given as %de; stereoselective reaction;
72%	With indium(III) chloride In acetonitrile for 0.0166667h; microwave irradiation;
70%	With iron(III) chloride In acetonitrile at 20℃; for 1h;

Reference： [1]Zhou, Jiafen; Chen, Heshan; Shan, Junjie; Li, Juan; Yang, Guofang; Chen, Xuan; Xin, Kunyun; Zhang, Jianbo; Tang, Jie [Journal of Carbohydrate Chemistry, 2014, vol. 33, # 6, p. 313 - 325]
[2]Bodipati, Naganjaneyulu; Palla, Srinivasa Rao; Komera, Venkateshwarlu; Peddinti, Rama Krishna [Tetrahedron Letters, 2014, vol. 55, # 50, p. 6878 - 6881]
[3]Gurawa, Aakanksha; Kashyap, Sudhir; Kumar, Manoj; Reddy, Thurpu Raghavender [Organic and biomolecular chemistry, 2020, vol. 18, # 25, p. 4848 - 4862]
[4]Shanmugasundaram, Bhagavathy; Bose, Ajay K.; Balasubramanian, Kalpattu K. [Tetrahedron Letters, 2002, vol. 43, # 38, p. 6795 - 6798]
[5]Sau, Abhijit; Palo-Nieto, Carlos; Galan, M. Carmen [Journal of Organic Chemistry, 2019, vol. 84, # 5, p. 2415 - 2424]
[6]De Melo, Adriana Cristina N.; De Oliveira, Ronaldo N.; De Freitas Filho, Joao R.; Da Silva, Teresinha G.; Srivastava, Rajendra M. [Heterocyclic Communications, 2017, vol. 23, # 3, p. 205 - 211]
[7]Misra, Anup Kumar; Tiwari, Pallavi; Agnihotri, Geetanjali [Synthesis, 2005, # 2, p. 260 - 266]
[8]Location in patent: experimental part Guchhait, Goutam; Misra, Anup Kumar [Catalysis Letters, 2011, vol. 141, # 7, p. 925 - 930]
[9]Roy, Rashmi; Rajasekaran, Parasuraman; Mallick, Asadulla; Vankar, Yashwant D. [European Journal of Organic Chemistry, 2014, vol. 2014, # 25, p. 5564 - 5573]
[10]Location in patent: scheme or table Rodríguez, Oscar Mariano; Colinas, Pedro Alfonso; Bravo, Rodolfo Daniel [Synlett, 2009, # 7, p. 1154 - 1156]
[11]Das, Saibal Kumar; Reddy, K. Anantha; Roy, Joyita [Synlett, 2003, # 11, p. 1607 - 1610]
[12]Masson; Soto; Bessodes [Synlett, 2000, # 9, p. 1281 - 1282]

23
[ 3240-34-4 ]
[ 4098-06-0 ]
[ 4163-60-4 ]

Yield	Reaction Conditions	Operation in experiment
89%	With boron trifluoride diethyl etherate In dichloromethane at -45 - -25℃; for 1h;

Reference： [1]Shi; Kim; Gin [Journal of the American Chemical Society, 2001, vol. 123, # 28, p. 6939 - 6940]

24
[ 64-19-7 ]
[ 4098-06-0 ]
[ 245730-35-2 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sodium periodate; copper(l) iodide at 20℃; Inert atmosphere; stereoselective reaction;	Typical experimental procedure for Iodoacetoxylation General procedure: A preformed solution of glycal (1a-1l) (1.0 equiv) in AcOH (0.5 mL) was treated with CuI (1.1 equiv) and NaIO4 (1.1 equiv) at room temperature. The reaction was stirred until the complete consumption of substrate. The reaction was diluted with EtOAc (10 mL), quenched with saturated NaHCO3 (5 mL), saturated aqueous sodium thoisulfate (2 mL) and extracted with EtOAC (3 X 30 mL). The combined organic layers were washed with brine solution, dried over anhydrous Na2SO4, concentrated in vacuo and purified by silica gel column chromatography to obtain the desired products (2a-2l). All products were fully characterised by 1H and 13C spectroscopy and MS/HRMS spectrometry and compared with that of literature data.
80%	With ammonium cerium(IV) nitrate; sodium iodide In acetonitrile at 0 - 23℃;
70%	Stage #1: acetic acid; triacetyl-D-galactal With ammonium cerium(IV) nitrate In acetonitrile at -15℃; Stage #2: With sodium iodide In acetonitrile at -15 - 25℃; for 4.5h;

64%	With N-iodo-succinimide In toluene at 100℃; for 0.166667h;
56%	With N-iodo-succinimide In toluene at 20℃; for 0.5h;	1, 3, 4, 6-Tetra-O-acetyl-2-deoxy-2-iodo-α-D-talose (1 b) NIS (58.0 mg, 0.260 mmol) and Acetic acid (0.500 ml) were added to a solutionof 3, 4, 6-tri-O-acetyl-D-galacal (54.0 mg, 0.200 mmol) in toluene(1.00 ml). The mixture was heated at room temperature for 0.5 h. Satd.Na2S2O3 was then added. The organic phase was collected, and the aqueous solution was extracted with EtOAc twice. The combined organic layerswere washed with satd. NaHCO3, brine, dried over Na2SO4, and filtered.The filtrate was concentrated in vacuo. The residue was purified by silicagel chromatography to give 1 b (47.3 mg, 56% yield) as a colorless syrup.1H NMR (400 MHz, CDCl3) d 6.49 (s, 1H, H-1), 5.41 (s, 1H, H-4), 4.88(dd, J4.0, 4.4 Hz, 1H, H-3), 4.38 (dd, J5.6, 6.8 Hz, 1H, H-5), 4.26 (d,J4.4 Hz, 1H, H-2), 4.17 (dd, J6.8 Hz, 2H, H-6a, H-6b), 2.17, 2.12, 2.07,2.03 (4 s, 12H, 4-COCH3). The spectroscopic data is identical to previouslyreported data.[49]

Reference： [1]Battina, Suresh Kumar; Kashyap, Sudhir [Tetrahedron Letters, 2016, vol. 57, # 7, p. 811 - 814]
[2]Roush; Narayan; Bennett; Briner [Organic letters, 1999, vol. 1, # 6, p. 895 - 897]
[3]Janczuk, Adam J.; Zhang, Wei; Andreana, Peter R.; Warrick, Joshua; Wang, Peng G. [Carbohydrate Research, 2002, vol. 337, # 14, p. 1247 - 1259]
[4]Wang, Hao; Tao, Jinyi; Cai, Xinpei; Chen, Wei; Zhao, Yueqi; Xu, Yang; Yao, Wang; Zeng, Jing; Wan, Qian [Chemistry - A European Journal, 2014, vol. 20, # 52, p. 17319 - 17323]
[5]Yao, Wang; Wang, Hao; Zeng, Jing; Wan, Qian [Journal of Carbohydrate Chemistry, 2021, vol. 40, # 7-9, p. 454 - 478]

25
[ 107-19-7 ]
[ 4098-06-0 ]
[ 158053-95-3 ]

Yield	Reaction Conditions	Operation in experiment
89%	With carbon immobilized iron (III) chloride hexahydrate In dichloromethane at 20℃; for 2h; stereoselective reaction;	General Experimental Procedure for the Synthesis of2,3-Unsaturated Galactosides General procedure: To a stirred solution of tri-O-acetyl-D-galactal (50 mg, 0.185 mmol) in DCM(1 mL) were added the corresponding alcohol (0.204 mmol, 1.1 equiv) andFeCl3·6H2O/C (50 mol%) at ambient temperature. After the reaction was completed(monitored by TLC), the reaction mixture was filtered and the catalystwas washed with dichloromethane. After evaporation of the solvent under vacuum,the crude products were purified by silica gel column chromatography(petroleum ether/EtOAc = 10/1).
76%	With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 50℃; for 1h; Inert atmosphere; stereoselective reaction;
70%	With indium(III) chloride In acetonitrile for 0.0166667h; microwave irradiation;

31%

With gold(III) chloride In dichloromethane at 20℃; for 24h;

Reference： [1]Zhou, Jiafen; Chen, Heshan; Shan, Junjie; Li, Juan; Yang, Guofang; Chen, Xuan; Xin, Kunyun; Zhang, Jianbo; Tang, Jie [Journal of Carbohydrate Chemistry, 2014, vol. 33, # 6, p. 313 - 325]
[2]Gurawa, Aakanksha; Kashyap, Sudhir; Kumar, Manoj; Reddy, Thurpu Raghavender [Organic and biomolecular chemistry, 2020, vol. 18, # 25, p. 4848 - 4862]
[3]Das, Saibal Kumar; Reddy, K. Anantha; Roy, Joyita [Synlett, 2003, # 11, p. 1607 - 1610]
[4]Location in patent: experimental part Balamurugan, Rengarajan; Koppolu, Srinivasa Rao [Tetrahedron, 2009, vol. 65, # 39, p. 8139 - 8142]

26
[ 4064-06-6 ]
[ 4098-06-0 ]
6-O-(4,6-di-O-acetyl-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl)-1,2:4,5-di-O-isopropylidene-α-D-galactopyranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris(pentafluorophenyl)borate In toluene at 75℃; for 2h; Sealed tube; stereoselective reaction;
72%	With trimethylsilyl trifluoromethanesulfonate; 1-(n-butyl)-3-methylimidazolium triflate at 20℃; for 1.66667h; stereoselective reaction;
66%	With carbon immobilized iron (III) chloride hexahydrate In dichloromethane at 20℃; for 3h; stereoselective reaction;	General Experimental Procedure for the Synthesis of2,3-Unsaturated Galactosides General procedure: To a stirred solution of tri-O-acetyl-D-galactal (50 mg, 0.185 mmol) in DCM(1 mL) were added the corresponding alcohol (0.204 mmol, 1.1 equiv) andFeCl3·6H2O/C (50 mol%) at ambient temperature. After the reaction was completed(monitored by TLC), the reaction mixture was filtered and the catalystwas washed with dichloromethane. After evaporation of the solvent under vacuum,the crude products were purified by silica gel column chromatography(petroleum ether/EtOAc = 10/1).

62%

With perchloric acid; silica gel In acetonitrile at 20℃; for 1h;

Reference： [1]Sau, Abhijit; Palo-Nieto, Carlos; Galan, M. Carmen [Journal of Organic Chemistry, 2019, vol. 84, # 5, p. 2415 - 2424]
[2]Location in patent: experimental part Guchhait, Goutam; Misra, Anup Kumar [Catalysis Letters, 2011, vol. 141, # 7, p. 925 - 930]
[3]Zhou, Jiafen; Chen, Heshan; Shan, Junjie; Li, Juan; Yang, Guofang; Chen, Xuan; Xin, Kunyun; Zhang, Jianbo; Tang, Jie [Journal of Carbohydrate Chemistry, 2014, vol. 33, # 6, p. 313 - 325]
[4]Misra, Anup Kumar; Tiwari, Pallavi; Agnihotri, Geetanjali [Synthesis, 2005, # 2, p. 260 - 266]

27
[ 67-63-0 ]
[ 4098-06-0 ]
isopropyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With perchloric acid; silica gel In acetonitrile at 20℃; for 2h;
82%	With carbon immobilized iron (III) chloride hexahydrate In dichloromethane at 20℃; for 2h; stereoselective reaction;	General Experimental Procedure for the Synthesis of2,3-Unsaturated Galactosides General procedure: To a stirred solution of tri-O-acetyl-D-galactal (50 mg, 0.185 mmol) in DCM(1 mL) were added the corresponding alcohol (0.204 mmol, 1.1 equiv) andFeCl3·6H2O/C (50 mol%) at ambient temperature. After the reaction was completed(monitored by TLC), the reaction mixture was filtered and the catalystwas washed with dichloromethane. After evaporation of the solvent under vacuum,the crude products were purified by silica gel column chromatography(petroleum ether/EtOAc = 10/1).
72%	With trimethylsilyl trifluoromethanesulfonate; 1-(n-butyl)-3-methylimidazolium triflate at 20℃; for 1.66667h; stereoselective reaction;

Reference： [1]Misra, Anup Kumar; Tiwari, Pallavi; Agnihotri, Geetanjali [Synthesis, 2005, # 2, p. 260 - 266]
[2]Zhou, Jiafen; Chen, Heshan; Shan, Junjie; Li, Juan; Yang, Guofang; Chen, Xuan; Xin, Kunyun; Zhang, Jianbo; Tang, Jie [Journal of Carbohydrate Chemistry, 2014, vol. 33, # 6, p. 313 - 325]
[3]Location in patent: experimental part Guchhait, Goutam; Misra, Anup Kumar [Catalysis Letters, 2011, vol. 141, # 7, p. 925 - 930]

28
[ 4098-06-0 ]
[ 318959-97-6 ]

Yield	Reaction Conditions	Operation in experiment
96%	With triethylsilane; boron trifluoride diethyl etherate In dichloromethane at 0℃; for 0.25h; Inert atmosphere;
94%	Stage #1: triacetyl-D-galactal With triethylsilane In dichloromethane at 0℃; for 0.0833333h; Stage #2: With boron trifluoride diethyl etherate In diethyl ether; dichloromethane for 1.5h;
94%	With triethylsilane; ruthenium trichloride In acetonitrile at 20℃; for 0.333333h; Inert atmosphere;	4.2. General procedure for the RuCl3-catalyzed C-glycosylation General procedure: To a stirred solution of glycal (1 equiv) and acceptor or carbon nucleophile (1.2 equiv) in anhydrous acetonitrile (2 mL/mmol) under an atmosphere of argon was added RuCl3 (5 mol %) at room temperature. The reaction mixture was stirred until the complete consumption of the starting material (glycal). The solvent wasconcentrated in vacuo, the crude residue was re-dissolved in dichloromethane and loaded on a silica gel column. The product was purified by silica gel chromatography using Hexane/EtOAc to afford the 2,3-unsaturated-C-glycosides in excellent yields. All theproducts were confirmed by IR, 1H NMR, 13C NMR and MS/HRMS spectroscopy, and overall spectroscopic data were in complete agreement with assigned structures and also compared with literature data.

88%	With triethylsilane; indium(III) chloride In acetonitrile for 0.00972222h; microwave irradiation;
87%	With PMHS In dichloromethane at 20℃; for 3.5h;
85%	With triethylsilane; perchloric acid In acetonitrile at 20℃; for 0.333333h;

Reference： [1]Jung, Sejin; Inoue, Asuka; Nakamura, Sho; Kishi, Takayuki; Uwamizu, Akiharu; Sayama, Misa; Ikubo, Masaya; Otani, Yuko; Kano, Kuniyuki; Makide, Kumiko; Aoki, Junken; Ohwada, Tomohiko [Journal of Medicinal Chemistry, 2016, vol. 59, # 8, p. 3750 - 3776]
[2]Grugel, Holger; Albrecht, Fabian; Minuth, Tobias; Boysen, Mike M. K. [Organic Letters, 2012, vol. 14, # 14, p. 3780 - 3783]
[3]Srinivas, Batthula; Reddy, Thurpu Raghavender; Kashyap, Sudhir [Carbohydrate Research, 2015, vol. 406, p. 86 - 92]
[4]Cohen, Jamie L.; Chamberlin, A. Richard [Tetrahedron Letters, 2007, vol. 48, # 14, p. 2533 - 2536]
[5]Yadav; Subba Reddy; Premalatha; Swamy [Tetrahedron Letters, 2005, vol. 46, # 15, p. 2687 - 2690]
[6]Tiwari, Pallavi; Agnihotri, Geetanjali; Misra, Anup Kumar [Carbohydrate Research, 2005, vol. 340, # 4, p. 749 - 752]

29
[ 7677-24-9 ]
[ 4098-06-0 ]
Acetic acid (2R,3R)-2-acetoxymethyl-6-cyano-3,6-dihydro-2H-pyran-3-yl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With perchloric acid In acetonitrile at 20℃; for 0.333333h;
62%	With ammonium cerium (IV) nitrate In acetonitrile at 20℃; for 12h; Inert atmosphere;	General procedure for Ferrier rearrangement of glycals by using CAN General procedure: A glycal (0.368 mmol) was dissolved in freshly dried CH3CN (3 mL) under N2 atmosphere. To this solution was added a nucleophile (0.736 mmol), followed by ceric ammonium nitrate (202 mg, 0.368 mmol). The reaction mixture was stirred at room temperature for the time indicated. After complete consumption of glycal (TLC monitoring), the reaction mixture was poured into a saturated NaHCO3 solution (5 mL), and extracted with ethyl acetate (3 × 5 mL). Combined organic extracts were washed with brine (1 × 10 mL), dried over Na2SO4, and concentrated under vacuum. The obtained residue was purified by column chromatography.

Reference： [1]Tiwari, Pallavi; Agnihotri, Geetanjali; Misra, Anup Kumar [Carbohydrate Research, 2005, vol. 340, # 4, p. 749 - 752]
[2]Ansari, Alafia A.; Reddy, Y. Suman; Vankar, Yashwant D. [Beilstein Journal of Organic Chemistry, 2014, vol. 10, p. 300 - 306]

30
[ 1520-70-3 ]
[ 4098-06-0 ]
4,6-di-O-acetyl-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl ethanesulfonamide [ No CAS ]
4,6-di-O-acetyl-2,3-dideoxy-β-D-threo-hex-2-enopyranosyl ethanesulfonamide [ No CAS ]

Reference： [1]Carbohydrate Research,2007,vol. 342,p. 2297 - 2302
[2]Synlett,2009,p. 1154 - 1156
[3]Tetrahedron Letters,2010,vol. 51,p. 5372 - 5374

31
penta-O-acetyl-α-D-galactopyranose [ No CAS ]
[ 4098-06-0 ]

Yield	Reaction Conditions	Operation in experiment
84%	Stage #1: penta-O-acetyl-α-D-galactopyranose With hydrogen bromide; acetic acid for 2h; Inert atmosphere; Stage #2: With disodium hydrogenphosphate; copper(II) sulfate; acetic acid; zinc In water for 1h;	Pentaaeetyi galactose (25,0 g, 64,0 mmol) was dissol ved in 33% HBr in HOAc (30 mL) and stirred under nitrogen for 2 hours. The reaction was diluted into EtOAc (500 mL) and washed with water (3x), saturated sodium bicarbonate (lx), and brine ( lx). The organic layer was dried over sodium sulfate and evaporated to give compound 1 as a pale yellow oil in quantitative yield. The compound was used without further purification. Compound 1 (26.34 g, 64.06 mmol) was dissolved in acetic acid (510 ml.) and zinc (67.01 g, 1024 mmol) added. The mixture was stirred vigorously A solution of CuS04 (2,96 g, 18,6 mmol) in aqueous NaH2P04 (128 mL, ,M, 1.53 g) was then added, and the reaction stirred for 1 hour. The reaction mixture was filtered over cclite and the resulting watcr/AcOH mixture evaporated to give a white solid. The white solid was dissolved m EtOAc (2x, 300 ml, each), water (300 mL), and EtOAc (lx, 300 mL). The layers were separated and the organic layer further washed wi th water (2x), saturated sodium bicarbonate (2x), and brine (lx). The organic solution was dried over sodium sulfate, evaporated, and purified on silica (15-25% EtOAc in Hexanes) to give compound 2 in 84% yield (14.64 g, 53.76 mmol). lH NMR (400 MHz, Chloroform ^ d 6.46 (dd, J - 6.3, 1.8 Hz, kH), 5.S4 (qd, J - 2.8, 1.2 Hz, 1H), 5.41 (dt, J- 4 1.7 Hz, IB), 4.71 (ddd, = 6.3 1.5 Hz, 1H), 4.33 (ddf, J- 7.0. 6, 1.4 Hz, 1 H), 4.29 - 4.15 (m, 2H), 2,11 (s, 3 H), 2.06 (s, 3H), 2.00 (s, 3H). C NMR (101 MHz, Chlorofom ) d 170.33, , 170.06, 169.97, 145.30, 98.80, 72.69, 63.82, 63.59, 61.85, 20.66, 20.64, 20.58.
	Multi-step reaction with 2 steps 1: 99 percent / HBr; acetic acid / 1.5 h / 20 °C 2: Zn; NMI / ethyl acetate / 2 h / Heating
	Multi-step reaction with 2 steps 1: TMS-Br / CH₂Cl₂ 2: 89 percent / (Cp₂TiCl)2 / tetrahydrofuran / Ambient temperature

Reference： [1]Current Patent Assignee: YALE UNIVERSITY - WO2019/199621, 2019, A1 Location in patent: Page/Page column 85-86
[2]Bay, Sylvie; Huteau, Valérie; Zarantonelli, Maria-Leticia; Pires, René; Ughetto-Monfrin, Joël; Taha, Muhamed-Kheir; England, Patrick; Lafaye, Pierre [Journal of Medicinal Chemistry, 2004, vol. 47, # 16, p. 3916 - 3919]
[3]Cavallaro, Cullen L.; Schwartz, Jeffrey [Journal of Organic Chemistry, 1995, vol. 60, # 21, p. 7055 - 7057]

32
[ 4098-06-0 ]
[ 120173-57-1 ]

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 2327 - 2342
[2]European Journal of Organic Chemistry,2011,p. 3685 - 3689
[3]Tetrahedron,2019,vol. 75

33
[ 4163-60-4 ]
[ 4098-06-0 ]

Yield	Reaction Conditions	Operation in experiment
75%	With hydrogen bromide; acetic acid In dichloromethane at 0 - 20℃; for 2h;
	Multi-step reaction with 2 steps 1: HBr / acetic acid; acetic anhydride / 1.) 0 deg C, 30 min, 2.) r.t., 2 h 2: Zn, N-methyl imidazole / ethyl acetate / 0.42 h / Heating
	Multi-step reaction with 2 steps 1: hydrogen bromide / dichloromethane 2: 1-methyl-1H-imidazole; zinc / ethyl acetate / Heating

	Multi-step reaction with 2 steps 1: hydrogen bromide; acetic anhydride; acetic acid / 12 h / 20 °C 2: sodium dihydrogenphosphate; zinc / acetone / 12 h / 20 °C
	Stage #1: β-D-galactose peracetate With hydrogen bromide; acetic acid In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere; Stage #2: With acetic acid; zinc In dichloromethane; water at -15 - 0℃; for 2h; Inert atmosphere;	General procedures for preparation of 3,4,6-tri-O-acetyl-D-glycals. General procedure: To a solution of O-acetyl-β-D-glycopyranose (10.0 g, 1.0 equiv) in CH2Cl2(100 mL) was added 33% HBr/AcOH (1.20 equiv) at 0 °C. The reaction solution was gradually warm up to room temperature and stirred for 2 hours under nitrogen atmosphere. Then the reaction mixture was quenched by NaHCO3and then transferred to a separation funnel. The organic layer was separated, and the aqueous layer was extracted with CH2Cl2(50 mL × 2). The organic layers were combined and washed with brine (100 mL × 2), dried over anhydrous MgSO4, filtered, and then concentrated under reduced pressure. The volatiles were removed in vacuo for 1 h. Then the crude compound dissolved in a solution of H2O (30 mL) and AcOH (60 mL) was slowly added activated Zn powder (1.0 equiv) at -15 °C. The reaction solution was stirred violently for 2 hours at 0 °C. The solution was filtered and then extracted with EtOAc (50 mL ×2) via a separation funnel. The combined organic layer was washed with NaHCO3 (50 mL × 2) and brine (50 mL × 2), dried over anhydrous MgSO4, filtered, and then concentrated under reduced pressure. The crude product was purified by flash column chromatography on silica gel and then the volatiles were removed in vacuo to obtain the product as colorless oil.
	Multi-step reaction with 2 steps 1: hydrogen bromide; acetic acid / dichloromethane / 0 - 20 °C 2: zinc; acetic acid / water / 0 - 20 °C
	Multi-step reaction with 2 steps 1: hydrogen bromide / acetic acid; dichloromethane / 1 h / 0 °C 2: ammonium chloride; zinc / acetonitrile / 4 h / 60 °C / Alkaline conditions

Reference： [1]Pilgrim, Wayne; Murphy, Paul V. [Organic Letters, 2009, vol. 11, # 4, p. 939 - 942]
[2]Broddefalk, Johan; Nilsson, Ulf; Kihlberg, Jan [Journal of Carbohydrate Chemistry, 1994, vol. 13, # 1, p. 129 - 132]
[3]Balcerzak, Anna K.; Ferreira, Sandra S.; Trant, John F.; Ben, Robert N. [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 4, p. 1719 - 1721]
[4]Zhang, Ying; Liu, Yang; Wang, Zhijun; Wang, Zhongfu; Huang, Linjuan [Journal of Chemical Research, 2012, vol. 36, # 4, p. 244 - 246]
[5]Hsu, Mei-Yuan; Liu, Yi-Pei; Lam, Sarah; Lin, Su-Ching; Wang, Cheng-Chung [Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 1758 - 1764]
[6]Chang, Chun-Wei; Wu, Chia-Hui; Lin, Mei-Huei; Liao, Pin-Hsuan; Chang, Chun-Chi; Chuang, Hsiao-Han; Lin, Su-Ching; Lam, Sarah; Verma, Ved Prakash; Hsu, Chao-Ping; Wang, Cheng-Chung [Angewandte Chemie - International Edition, 2019, vol. 58, # 47, p. 16775 - 16779][Angew. Chem., 2019, vol. 131, # 47, p. 16931 - 16935,5]
[7]Chapa-Villarreal, Fabiola A.; Chiaramonte, Jonathan; Piazza, Sabrina M.; Reynolds, Michael R.; Trant, John F.; Xu, Peihan [New Journal of Chemistry, 2021, vol. 45, # 41, p. 19224 - 19227]

34
[ 10257-28-0 ]
[ 108-24-7 ]
[ 4098-06-0 ]

Yield	Reaction Conditions	Operation in experiment
79%	Stage #1: D-Galactose; acetic anhydride With perchloric acid at 0 - 20℃; for 3h; Stage #2: With hydrogen bromide; acetic acid at 0 - 20℃; for 8h; Stage #3: With sodium dihydrogenphosphate; zinc In acetone at 20℃; for 12h;
78.3%	Stage #1: D-Galactose; acetic anhydride With perchloric acid at 0 - 20℃; for 0.5h; Stage #2: With hydrogen bromide; acetic acid at 20℃; for 7.5h; Cooling with ice; Stage #3: With sodium dihydrogenphosphate; zinc In acetone at 20℃; for 8.5h;	3 Compound 22: D-galactose (20 g, 111 mmol) was added to a 500 mL round bottom flask followed by acetic anhydride(80 mL), the reaction was placed in an ice water bath, and the reaction temperature was lowered to 0 ° C.After stirring uniformly, 3 drops of perchloric acid were added dropwise, and the temperature was slowly raised to room temperature. After 30 minutes of reaction, the solution became clear.After TLC was used to monitor the reaction of the starting material, the reaction mixture was poured into 1 L of ice water, and extracted with dichloromethane (5×100 mL). The organic phase was combined and washed with saturated sodium hydrogen carbonate solution until no bubbles were formed, and saturated brine (100 mL) After washing, it was dried over anhydrous sodium sulfate and concentrated under reduced pressure to reduce solvent to 200 mL. Under ice water bath cooling conditions, 80 mL of hydrogen bromide-acetic acid solution (33% w/w) was added, and the mixture was slowly added dropwise, and the addition was completed in 30 minutes, and the temperature was slowly raised to room temperature for 7 hours. After the TLC was monitored, the reaction mixture was completely diluted with dichloromethane (200 mL), washed with ice water (2×150 mL), and washed with saturated sodium hydrogen carbonate solution until no bubbles were formed, and washed with saturated brine (100 mL). Dry over sodium sulfate, concentrate by rotary evaporation and dry in vacuo.Ace (200 mL) was added to the dried crude product to dissolve, sodium dihydrogen phosphate (200 mL) was added, and then 80 g of zinc powder was slowly added thereto, and the addition was completed in 30 minutes, and the reaction was carried out at room temperature for 8 hours.After the TLC was used to monitor the reaction of the starting material, the mixture was filtered through celite, and the filtrate was extracted with ethyl acetate (3×150 mL). The organic layer was combined. Water Na2SO4 was dried, concentrated under reduced pressure, and the residue was appliedColumn chromatography (PE: EA=6:1→4:1→3:1)Purified colorless syrup 22 (23.5 g, 78.3%).
66%	Stage #1: D-Galactose; acetic anhydride With hydrogen bromide; acetic acid at 0 - 20℃; Stage #2: With sodium acetate; copper(II) sulfate; acetic acid; zinc In water at 15 - 20℃; for 2h;

Stage #1: D-Galactose; acetic anhydride Stage #2: With phosphorus; bromine Stage #3: With zinc

Reference： [1]Zhang, Shuo; Niu, You-Hong; Ye, Xin-Shan [Organic Letters, 2017, vol. 19, # 13, p. 3608 - 3611]
[2]Current Patent Assignee: JIANGNAN UNIVERSITY - CN108530497, 2018, A Location in patent: Paragraph 0074; 0076; 0079
[3]Maiti, Dilip K.; Halder, Samiran; Pandit, Palash; Chatterjee, Nirbhik; De Joarder, Dripta; Pramanik, Nabyendu; Saima, Yasmin; Patra, Amarendra; Maiti, Prabir K. [Journal of Organic Chemistry, 2009, vol. 74, # 21, p. 8086 - 8097]
[4]Ram, Ram N.; Kumar, Neeraj; Gupta, Dharmendra Kumar [Advanced Synthesis and Catalysis, 2017, vol. 359, # 3, p. 432 - 442]

35
[ 226384-14-1 ]
[ 4098-06-0 ]
[ 1233711-61-9 ]

Yield	Reaction Conditions	Operation in experiment
20%	With lithium bromide In acetonitrile at 20℃; for 12h; Molecular sieve;	1 Example 1Preparation of acetylated galactoside Ia; Into a solution of hydroxyketone 4 (110 mg; 0.2 mmol) in dry acetonitrile (6 ml), acetate of D-galactal (0.25 mmol), molecular sieve 4A (100 mg), lithium bromide (150 mg) and Amberlyst 15 in H+-cycle (180 mg) were added. The reaction mixture was stirred at room temperature for 12 hours. The course of the reaction was observed by TLC. The reaction mixture was then filtered over a kieselguhr layer and the column was washed with ethyl acetate. The filtrate was diluted with water, extracted with ethyl acetate and the organic phase was evaporated at a rotary vacuum evaporator (RVO). The evaporation residue was dissolved in chloroform and the solution was poured over a short column of silica gel (elution by ethyl acetate). The eluate was evaporated at an RVO. The crude product was then separated by HPLC, with mixture of ethyl acetate and hexane in the volume ration of 5:4 as the mobile phase. Lyofilization from t- BuOH gave white lyofilisate Ia (33 mg; 20 %). [α]D +23.3x10"' deg cm2 g"1 (c = 0.41 g/100 ml)13C NMR: 15.88 (C27), 16.50 (C24), 16.73 (C26), 16.83 (C25), 18.08 (C6), 20.00 (C29), 20.52 (C30), 20.71 (AcO: CH3 4), 20.76 (AcO: CH3 3), 20.83 (AcO: CH3 2), 21.28 (CI l), 21.29 (AcO: CH3 1), 23.58 (C2), 25.14 (C20), 27.36 (C15), 27.77 (C12), 27.88 (C23), 29.96 (C2'), 32.03 (C16), 34.74 (C7), 37.09 (ClO), 37.72 (C4), 38.52 (Cl), 41.32 (C8), 42.74 (C13), 45.52 (C14), 46.06 (C17), 48.14 (C22), 50.90 (C9), 55.37 (C5), 62.14 (C6'), 65.35 (C3'), 65.98 (C4'), 66.82 (C5'), 70.81 (C28), 80.66 (C3), 97.77 (Cl '), 146.35 (C19), 169.96 (AcO: C=O 4), 170.23 (AcO: C=O 3), 170.42 (AcO: C=O 2), 170.98 (C18), 172.48 (AcO: C=O 1), 208.24 (C21)
20%	With lithium bromide In acetonitrile at 20℃; molecular sieve 4 A;	1 Preparation of Acetylated Galactoside 1aInto a solution of hydroxyketone 4 (110 mg; 0.2 mmol) in dry acetonitrile (6 ml), acetate of D-galactal (0.25 mmol), molecular sieve 4 A (100 mg), lithium bromide (150 mg) and Amberlyst 15 in H+-cycle (180 mg) were added. The reaction mixture was stirred at room temperature for 12 hours. The course of the reaction was observed by TLC. The reaction mixture was then filtered over a kieselguhr layer and the column was washed with ethyl acetate. The filtrate was diluted with water, extracted with ethyl acetate and the organic phase was evaporated at a rotary vacuum evaporator (RVO). The evaporation residue was dissolved in chloroform and the solution was poured over a short column of silica gel (elution by ethyl acetate). The eluate was evaporated at an RVO. The crude product was then separated by HPLC, with mixture of ethyl acetate and hexane in the volume ration of 5:4 as the mobile phase. Lyofilization from t-BuOH gave white lyofilisate 1a (33 mg; 20%). [α]D+23.3×10-1 deg cm2 g-1 (c=0.41 g/100 ml)13C NMR: 15.88 (C27), 16.50 (C24), 16.73 (C26), 16.83 (C25), 18.08 (C6), 20.00 (C29), 20.52 (C30), 20.71 (AcO: CH3 4), 20.76 (AcO: CH3 3), 20.83 (AcO: CH3 2), 21.28 (C11), 21.29 (AcO: CH3 1), 23.58 (C2), 25.14 (C20), 27.36 (C15), 27.77 (C12), 27.88 (C23), 29.96 (C2'), 32.03 (C16), 34.74 (C7), 37.09 (C10), 37.72 (C4), 38.52 (C1), 41.32 (C8), 42.74 (C13), 45.52 (C14), 46.06 (C17), 48.14 (C22), 50.90 (C9), 55.37 (C5), 62.14 (C6'), 65.35 (C3'), 65.98 (C4'), 66.82 (C5'), 70.81 (C28), 80.66 (C3), 97.77 (C1'), 146.35 (C19), 169.96 (AcO: CO 4), 170.23 (AcO: CO 3), 170.42 (AcO: CO 2), 170.98 (C18), 172.48 (AcO: CO 1), 208.24 (C21)
20%	With lithium bromide In acetonitrile at 20℃; for 12h; Molecular sieve;

Reference： [1]Current Patent Assignee: PALACKY UNIVERSITY OLOMOUC - WO2010/54606, 2010, A2 Location in patent: Page/Page column 12-14
[2]Current Patent Assignee: PALACKY UNIVERSITY OLOMOUC - US2011/218167, 2011, A1 Location in patent: Page/Page column 4
[3]Perlikova, Pavla; Kvasnica, Miroslav; Urban, Milan; Hajduch, Marian; Sarek, Jan [Bioconjugate Chemistry, 2019, vol. 30, # 11, p. 2844 - 2858]

36
[ 374902-53-1 ]
[ 4098-06-0 ]
[ 1233711-69-7 ]

Yield	Reaction Conditions	Operation in experiment
47%	With lithium bromide In acetonitrile at 20℃; for 12h; Molecular sieve;	3 Example 3Preparation of acetylated galactoside 2b; Into a solution of hydroxymethyl ester 2a (500 mg; 1 mmol) in dry acetonitrile (30 ml), acetate of D-galactal (1.2 mmol), molecular sieve 4A (500 mg), lithium bromide (730 mg) and Amberlyst 15 in H+-cycle (900 mg) were added. The reaction mixture was stirred at room temperature for 12 hours. The course of the reaction was observed by TLC. The reaction mixture was then filtered throut a kieselguhr layer and the column was washed with ethyl acetate. The filtrate was diluted with water, extracted with ethyl acetate and the organic phase was evaporated at an RVO. The evaporation residue was dissolved in chloroform and the solution was poured over a short column of silica gel (elution by ethyl acetate). The eluate was evaporated at an RVO. The crude product was then separated by HPLC. White lyofilisate (t-BuOH) 2b was obtained (360 mg; 47 %). [α]D +38.9x10"' deg cm2 g"1 (c = 0.52 g/100 ml)13C NMR: 15.89 (C27), 16.31 (C24), 16.64 (C26), 16.76 (C25), 18.14 (C6), 19.98 (C29), 20.10 (C30), 20.73 (AcO: CH3 3), 20.77 (AcO: CH3 2), 20.90 (AcO: CH3 1), 21.19 (CI l), 21.96 (C2), 25.08 (C20), 27.64 (C12), 28.50 (C23), 29.08 (C15), 30.73 (C2'), 33.66 (C16), 34.89 (C7), 37.12 (ClO), 38.40 (C4), 38.51 (Cl), 41.27 (C8), 45.15 (C13), 45.16 (C14), 47.60 (C22), 51.11 (C9), 52.48 (COOCH3), 53.05 (C17), 55.74 (C5), 62.47 (C6'), 66.39 (C3'), 66.75 (C4'), 67.02 (C5'), 82.63 (C3), 93.64 (Cl '), 145.66 (C19), 170.10 (AcO: C=O 3), 170.33 (AcO: C=O 2), 170.43 (AcO: C=O 1), 171.83 (C18), 174.83 (C28), 207.29 (C21)
47%	With lithium bromide In acetonitrile at 20℃; for 12h; molecular sieve 4 A;	3 Preparation of 2-deoxyglucosides 1b a 1c: a: tri-O-acetylglucal, LiBr, Amberlyst 15, Molecular Sieve 4 A/CH3CN Example 3 Preparation of Acetylated Galactoside 2b Into a solution of hydroxymethyl ester 2a (500 mg; 1 mmol) in dry acetonitrile (30 ml), acetate of D-galactal (1.2 mmol), molecular sieve 4 A (500 mg), lithium bromide (730 mg) and Amberlyst 15 in H+-cycle (900 mg) were added. The reaction mixture was stirred at room temperature for 12 hours. The course of the reaction was observed by TLC. The reaction mixture was then filtered through a kieselguhr layer and the column was washed with ethyl acetate. The filtrate was diluted with water, extracted with ethyl acetate and the organic phase was evaporated at an RVO. The evaporation residue was dissolved in chloroform and the solution was poured over a short column of silica gel (elution by ethyl acetate). The eluate was evaporated at an RVO. The crude product was then separated by HPLC. White lyofilisate (t-BuOH) 2b was obtained (360 mg; 47%). [α]D+38.9*10-1 deg cm2 g-1 (c=0.52 g/100 ml) 13C NMR: 15.89 (C27), 16.31 (C24), 16.64 (C26), 16.76 (C25), 18.14 (C6), 19.98 (C29), 20.10 (C30), 20.73 (AcO: CH3 3), 20.77 (AcO: CH3 2), 20.90 (AcO: CH3 1), 21.19 (C11), 21.96 (C2), 25.08 (C20), 27.64 (C12), 28.50 (C23), 29.08 (C15), 30.73 (C2'), 33.66 (C16), 34.89 (C7), 37.12 (C10), 38.40 (C4), 38.51 (C1), 41.27 (C8), 45.15 (C13), 45.16 (C14), 47.60 (C22), 51.11 (C9), 52.48 (COOCH3), 53.05 (C17), 55.74 (C5), 62.47 (C6'), 66.39 (C3'), 66.75 (C4'), 67.02 (C5'), 82.63 (C3), 93.64 (C1'), 145.66 (C19), 170.10 (AcO: C=O 3), 170.33 (AcO: C=O 2), 170.43 (AcO: C=O 1), 171.83 (C18), 174.83 (C28), 207.29 (C21)
47%	With lithium bromide In acetonitrile at 20℃; for 12h; Molecular sieve;

Reference： [1]Current Patent Assignee: PALACKY UNIVERSITY OLOMOUC - WO2010/54606, 2010, A2 Location in patent: Page/Page column 15-16
[2]Current Patent Assignee: PALACKY UNIVERSITY OLOMOUC - US2011/218167, 2011, A1 Location in patent: Page/Page column 6
[3]Perlikova, Pavla; Kvasnica, Miroslav; Urban, Milan; Hajduch, Marian; Sarek, Jan [Bioconjugate Chemistry, 2019, vol. 30, # 11, p. 2844 - 2858]

37
[ 3144-09-0 ]
[ 4098-06-0 ]
[ 1254049-82-5 ]

Yield	Reaction Conditions	Operation in experiment
79%	With ruthenium trichloride In acetonitrile at 20℃; for 0.666667h; Inert atmosphere;	General procedure for the RuCl₃-catalyzed N-glycosylation. General procedure: To a stirred solution of glycal (1.0 equiv) and N-nucleophile (1.2 equiv) in anhydrous acetonitrile (2 mL/mmol) under an atmosphere of argon was added RuCl3 (5 mol%) at room temperature. The reaction mixture was stirred until the complete consumption of the glycal as indicated by TLC. The reaction mixture was concentrated in vacuo, the crude residue was re-dissolved in dichloromethane and loaded on a silica gel column. The product was purified by silica gel chromatography using Hexane/EtOAc to afford the 2,3-unsaturated-N-glycosides as an inseparable α/β mixture or α-anomer in case of 3g,3g,3l.
75%	With Amberlyst 15 In acetonitrile at 20℃; for 0.666667h; optical yield given as %de; diastereoselective reaction;

Reference： [1]Reddy, Thurpu Raghavender; Chittela, Sravanthi; Kashyap, Sudhir [Tetrahedron, 2014, vol. 70, # 48, p. 9224 - 9229]
[2]Location in patent: experimental part Témpera, Carlos A.; Colinas, Pedro A.; Bravo, Rodolfo D. [Tetrahedron Letters, 2010, vol. 51, # 41, p. 5372 - 5374]

38
[ 4098-06-0 ]
[ 116783-35-8 ]

Reference： [1]European Journal of Organic Chemistry,2011,p. 3685 - 3689
[2]ChemBioChem,2018,vol. 19,p. 1142 - 1146
[3]Beilstein Journal of Organic Chemistry,2019,vol. 15,p. 1581 - 1591
[4]Tetrahedron,2019,vol. 75

39
[ 570-02-5 ]
[ 4098-06-0 ]
[ 1323988-63-1 ]

Reference： [1]Organic Letters,2011,vol. 13,p. 4608 - 4611

40
[ 1666-13-3 ]
[ 4064-06-6 ]
[ 4098-06-0 ]
[ 1414875-52-7 ]

Yield	Reaction Conditions	Operation in experiment
72%	With N-Bromosuccinimide In acetonitrile at 20℃; for 0.666667h; stereoselective reaction;	23 To a solution of tri-O-acetyl-d-glucal (1; 545 mg, 2.0 mmol) in CH3CN (5 mL) were added alcohol (4.0 mmol) or monosaccharide acceptor (2.5 mmol), diphenyl diselenide (750 mg, 2.40 mmol), and NBS (550 mg, 3.09 mmol) and the reaction mixture was allowed to stir at room temperature for appropriate time as mentioned in Table 1. The reaction mixture was diluted with water and extracted with CH2Cl2. The organic layer was successively washed with satd. NaHCO3, water, dried (Na2SO4), and concentrated under reduced pressure. The crude product was purified over SiO2 using hexane-EtOAc as eluant to give pure individual isomer. Spectral data of the isolated products are presented below. 4.2.23 3,4,6-Tri-O-acetyl-2-deoxy-2-phenylselenyl-α-d-talopyranosyl-(1→6)-1,2:3,4-di-O-isopropylidene-α-d-galactopyranose (35) Colorless oil; +1 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz): δ 7.53-7.24 (m, 5H, Ar-H), 5,46 (d, J = 5.0 Hz, 1H, H-1A), 5.43 (dd, J = 5.0, 3.0 Hz, 1H, H-3B), 5.33 (br s, 1H, H-4B), 5.22 (br s, 1H, H-1B), 4.54 (dd, J = 7.5, 2.0 Hz, 1H, H-4A), 4.35-4.33 (m, 1H, H-5B), 4.27-4.26 (m, 1H, H-2A), 4.20-4.16 (m, 1H, H-6aB), 4.13-4.09 (m, 2H, H-3A, H-6bB), 3.91-3.86 (m, 1H, H-5A), 3.76-3.61 (m, 2H, H-6abA), 3.56-3.55 (m, 1H, H-2B), 2.22, 2.08, 2.07 (3 s, 9H, 3 COCH3), 1.48, 1.34, 1.30, 1.24 (4 CH3); 13C NMR (CDCl3, 125 MHz): δ 170.1, 169.9, 169.7 (3 COCH3), 133.7-127.6 (Ar-C), 109.3, 108.6 (2 C(CH3)2), 101.8 (C-1B), 96.1 (C-1A), 70.9 (C-3A), 70.6 (C-4A), 70.5 (C-2A), 76.1 (C-3B), 66.9 (C-5B), 66.5 (C-4B), 66.4 (C-5A), 66.2 (C-6A), 62.0 (C-6B), 46.2 (C-2B), 26.1, 25.9, 24.9, 24.5, (4 CH3), 21.0, 20.9, 20.7 (3 COCH3); ESI-MS: 551.1 [M+Na]+; Anal. Calcd for C30H40O13Se (688.16): C, 52.40; H, 5.86. Found: C, 52.22; H, 6.10.

Reference： [1]Sau, Abhijit; Misra, Anup Kumar [Carbohydrate Research, 2012, vol. 361, p. 41 - 48,8]

41
[ 53008-65-4 ]
[ 1666-13-3 ]
[ 4098-06-0 ]
[ 1414875-53-8 ]

Yield	Reaction Conditions	Operation in experiment
70%	With N-Bromosuccinimide In acetonitrile at 20℃; for 0.666667h; stereoselective reaction;	24 To a solution of tri-O-acetyl-d-glucal (1; 545 mg, 2.0 mmol) in CH3CN (5 mL) were added alcohol (4.0 mmol) or monosaccharide acceptor (2.5 mmol), diphenyl diselenide (750 mg, 2.40 mmol), and NBS (550 mg, 3.09 mmol) and the reaction mixture was allowed to stir at room temperature for appropriate time as mentioned in Table 1. The reaction mixture was diluted with water and extracted with CH2Cl2. The organic layer was successively washed with satd. NaHCO3, water, dried (Na2SO4), and concentrated under reduced pressure. The crude product was purified over SiO2 using hexane-EtOAc as eluant to give pure individual isomer. Spectral data of the isolated products are presented below. 4.2.24 Methyl (3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-α-d-talopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-d-glucopyranoside (36) Colorless oil; +7 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz): δ 7.57-7.19 (m, 20 H, Ar-H), 5.38 (dd, J = 5.0, 3.0 Hz, 1H, H-3B), 5.28 (br s, 1H, H-4B), 5.22 (br s, 1H, H-1B), 4.95-4.54 (6 d, J = 11.0 Hz each, 6H, PhCH2), 4.41 (d, J = 3.5 Hz, 1H, H-1A), 4.17-4.15 (m, 1H, H-5B), 4.12-4.00 (m, 2H, H-6abB), 3.92 (t, J = 9.5 Hz each, 1H, H-4A), 3.69-3.61 (m, 3H, H-5A, H-6abA), 3.49-3.48 (m, 1H, H-2B), 3.36-3.32 (m, 2H, H-2A, H-3A), 3.30 (s, 3H, OCH3), 2.20, 2.08, 1.97 (3 s, 9H, 3 COCH3); 13C NMR (CDCl3, 125 MHz): δ 170.1, 169.9, 169.8, (3 COCH3), 138.6-127.6 (Ar-C), 101.9 (C-1B), 97.7 (C-1A), 82.1 (C-4A), 80.1 (C-3A), 77.6 (C-2A), 75.7 (PhCH2), 74.8 (PhCH2), 73.2 (PhCH2), 69.7 (C-5A), 66.9 (C-3B), 66.7 (C-4B), 66.4 (C-5B), 66.0 (C-6A), 62.0 (C-6B), 55.0 (OCH3), 46.2 (C-2B), 21.0, 20.9, 20.6 (3 COCH3); ESI-MS: 915.2 [M+Na]+; Anal. Calcd for C46H52O13Se (892.25): C, 61.95; H, 5.88. Found: C, 61.76; H, 6.10.

Reference： [1]Sau, Abhijit; Misra, Anup Kumar [Carbohydrate Research, 2012, vol. 361, p. 41 - 48,8]

42
[ 100-49-2 ]
[ 4098-06-0 ]
[ 1415013-47-6 ]
[ 1415013-48-7 ]

Reference： [1]Catalysis Letters,2013,vol. 143,p. 169 - 175

43
[ 100-49-2 ]
[ 4098-06-0 ]
[ 1415013-47-6 ]
[ 1415013-48-7 ]
cyclohexylmethyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-threoes-2-enopyranoside [ No CAS ]

Reference： [1]Catalysis Letters,2013,vol. 143,p. 169 - 175

44
[ 1400585-44-5 ]
[ 4098-06-0 ]
[ 1423016-76-5 ]

Yield	Reaction Conditions	Operation in experiment
83%	Stage #1: (S) 4-isopropyl-N-(2-pivaloyloxyacetyl)-1,3-thiazolidine-2-thione With titanium tetrachloride In dichloromethane at 0℃; for 0.0833333h; Stage #2: With N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; for 0.5h; Stage #3: triacetyl-D-galactal With tin(IV) chloride In dichloromethane at 0℃; for 5h; diastereoselective reaction;	Typical experimental procedure: General procedure: Neat TiCl4 (0.12 mL,1.1 mmol) is added dropwise to a solution of 1 (303 mg, 1.0 mmol) in CH2Cl2 (4 mL), at 0 °C. The orange suspension is stirred for 5 min at 0 °C, and a solution of i-Pr2NEt (0.19 mL, 1.1 mmol) in CH2Cl2 (1.5 mL) is added. The dark brown solution is stirred for 30 min at 0 °C. Then, a 1 M SnCl4 solution in CH2Cl2 (0.55 mL, 0.55 mmol) is carefully added, followed 5 min later by a 0.5 M solution of the glycal (1 mL, 0.5 mmol) and the resulting mixture is stirred for 5 h at 0 °C. The reaction is quenched by the addition of satd NH4Cl, extracted with CH2Cl2 and the combined extracts were dried and concentrated. The residue is finally purified by column chromatography with deactivated silica gel (2.5% Et3N) to afford pure adducts 2.

Reference： [1]Gálvez, Erik; Sau, Miriam; Romea, Pedro; Urpí, Fèlix; Font-Bardia, Mercè [Tetrahedron Letters, 2013, vol. 54, # 11, p. 1467 - 1470]

45
[ 536-74-3 ]
[ 4098-06-0 ]
[ 879906-21-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	With trimethylsilyl trifluoromethanesulfonate In dichloromethane at -20℃;
88%	Stage #1: phenylacetylene With ethyl bromoacetate; zinc In dichloromethane at 40℃; for 1h; Inert atmosphere; Stage #2: triacetyl-D-galactal In dichloromethane at 40℃; Inert atmosphere; stereoselective reaction;
82%	With trimethylsilyl trifluoromethanesulfonate In dichloromethane at -20℃; for 0.0333333h; stereoselective reaction;	Typical Procedure C-alkynylation of Glycals General procedure: To a mixture of glucal (1 equiv) and alkyne (1.2 equiv) in DCM at -20 °C, was added TMSOTf (50 mol %) and kept on stirring till completion of reaction as monitored on TLC. The reaction was quenched with sat. NaHCO3 solution and extracted with DCM (twice), washed with sat. brine and purified over silica gel (100-200 mesh) using hexane:EtOAc as eluent to afford pure products.

70%	With copper(II) bis(trifluoromethanesulfonate); ascorbic acid In acetonitrile at 20℃; for 0.133333h; diastereoselective reaction;
70%	With trimethylsilyl trifluoromethanesulfonate In 1,2-dichloro-ethane at 80℃; for 0.333333h; Inert atmosphere; Molecular sieve; stereoselective reaction;	Typical procedure for the synthesis of C-alkynylglycosides General procedure: A mixture of 3,4,6-tri-O-acetyl-D-glucal (40.8 mg,0.15 mmol), 4 Å molecular sieves (60 mg) and phenylacetylene (19.8 uL, 0.18 mmol, 1.2 equiv) in dry dichloroethane (2 mL) at 80 °C under nitrogen atmosphere was added the TMSOTf (16.2 uL, 0.09 mmol), The reaction mixture was stirred at 80 °C for 25 min. After complete conversion, as indicated by TLC analysis, the reaction mixture was diluted with dichloromethane(8 mL) and quenched with saturated NaHCO3 (8 mL). The layers were partitioned and the aqueous layer was extracted with dichloromethane (2 × 8 mL). The combined organic layers were washed with saturated NaHCO3 (12 mL) and saturated brine (12 mL), then dried over anhydrous Na2SO4. After evaporation of the solvent under reduced pressure, the crude product was purified by column chromatography on silica gel (ethyl acetate - petroleum ether =1:12) affording 1a (31.6 mg, 67 % yield). 1-(4,6-di-O-acetyl-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl)-2-phenylacetylene (6a). 1H NMR (500 MHz, CDCl3) δ 7.44 (dd, J = 7.6, 1.8 Hz, 2H), 7.37-7.29 (m, 3H), 6.15 (dd, J = 10.0, 3.8 Hz, 1H), 6.06 (ddd, J = 10.0, 5.4, 1.8 Hz, 1H), 5.27 (dd, J = 3.6, 1.9 Hz, 1H), 5.12 (dd, J = 5.4, 2.3 Hz, 1H), 4.44 (ddd, J = 7.4, 5.3, 2.4 Hz, 1H), 4.32 (dd, J = 11.5, 5.2 Hz, 1H), 4.22 (dd, J = 11.5, 7.3 Hz, 1H), 2.10 (s, 3H), 2.08 (s, 3H). HRMS (ESI): m/z Calculated for [M + Na]+ C18H18O5Na 337.1046, found 337.1050.

Reference： [1]Madhubabu, Tatina; Yousuf, Syed Khalid; Kusunuru, Anil Kumar; Mukherjee, Debaraj [European Journal of Organic Chemistry, 2014, vol. 2014, # 33, p. 7333 - 7338]
[2]Tatina, Madhu Babu; Kusunuru, Anil Kumar; Yousuf, Syed Khalid; Mukherjee, Debaraj [Organic and Biomolecular Chemistry, 2014, vol. 12, # 40, p. 7900 - 7903]
[3]Devari, Shekaraiah; Kumar, Manjeet; Deshidi, Ramesh; Rizvi, Masood; Shah, Bhahwal Ali [Beilstein Journal of Organic Chemistry, 2014, vol. 10, p. 2649 - 2653]
[4]Kusunuru, Anil Kumar; Tatina, Madhubabu; Yousuf, Syed Khalid; Mukherjee, Debaraj [Chemical Communications, 2013, vol. 49, # 86, p. 10154 - 10156]
[5]Chen, Heshan; Luo, Xiaosheng; Qiu, Saifeng; Sun, Wengjie; Zhang, Jianbo [Glycoconjugate Journal, 2017, vol. 34, # 1, p. 13 - 20]

46
[ 4098-06-0 ]
[ 96744-57-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	With N-chloro-succinimide; triphenylphosphine In dichloromethane at 20℃; diastereoselective reaction;	8 General procedure for 1,2-dichlorination of glycals General procedure: To a solution of the glycal (100mg) in CH2Cl2 (3mL) was added PPh3 (1.5equiv) followed by NCS (3.0equiv) over a period of 5min. After stirring for 3-4h at room temperature, the completion of reaction was checked by TLC. Then the mixture was treated with saturated NaHCO3, poured into a separatory funnel, and extracted with DCM. The separated organic phase was washed with sodium thiosulphate to remove Cl2, dried over Na2SO4, filtered, and concentrated. The residue was purified by 60-120 silica gel column chromatography (EtOAc/hexane) to yield the chlorinated products (88-90%) as colorless syrups. 4.8 Preparation and spectral data of 3,4,6-tri-O-acetyl-2-chloro-2-deoxy-α-glalactopyranosyl chloride (2f) Prepared by the general procedure for dichlorination of glycals by using 1f (100 mg, 0.37 mmol), NCS (147 mg, 3 equiv.), and PPh3 (145 mg, 1.5 equiv) to yield the desired product 2f as semisolid (89% yield); Rf (20% EtOAc/hexane) 0.6; +154 (c 1.0, CHCl3); IR (CHCl3) 1744, 772 cm-1; 1H NMR (400 MHz, CDCl3) δ 6.21 (d, J=3.6 Hz, 1H), 5.50 (d, J=3.0 Hz, 1H), 5.38 (dd, J=11.1, 3.2 Hz, 1H), 4.61 (t, J=6.4 Hz, 1H), 4.44 (dd, J=11.0, 3.6 Hz, 1H), 4.18-4.06 (m, 2H), 2.15 (s, 3H), 2.06 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 170.4, 169.8, 169.6, 93.6, 69.8, 69.2, 67.5, 60.9, 55.4, 20.7, 20.6, 20.5, ESI MS (m/z): 342 [M]+. Anal. Calcd for C12H16Cl2O7: C, 42.00; H, 4.70. Found C, 41.92; H, 4.67.

Reference： [1]Hussain, Altaf; Mukherjee, Debaraj [Tetrahedron, 2014, vol. 70, # 6, p. 1133 - 1139]

47
[ 118358-66-0 ]
[ 4098-06-0 ]
[ 1463469-27-3 ]
O-(4,6-di-O-acetyl-2,3-dideoxy-β-D-lyxo-hex-2-enopyranosyl)-N-(9-fluorenylmethoxycarbonyl)-L-serine benzyl ester [ No CAS ]

Reference： [1]Chemical Papers,2014,vol. 68,p. 525 - 530

48
[ 4098-06-0 ]
[ 1554363-74-4 ]

Yield	Reaction Conditions	Operation in experiment
82%	With N-iodo-succinimide; silver nitrate In acetonitrile at 80℃; for 3h; Inert atmosphere;
56%	With N-iodo-succinimide; silver nitrate In acetonitrile at 80℃; Inert atmosphere;	Synthesis of 3,4,6-tri-O-acetyl-2-iodo-D-glucal and 3,4,6-tri-O-acetyl-2-iodo-D-galactal (4 and 5) General procedure: in a two-necked round-bottom flask was added3.67 mmol (1 g) of 3,4,6-tri-O-acetyl-glycal, followed by 7 mL of dry CH3CN,under nitrogen flow. The solution was heated up to 80 C and 4.44 mmol (1 g)of NIS and 2.94 mmol (500mg) of AgNO3 were added to the reaction mixtureand kept with good stirring. After consumption of the substrate (monitored byTLC), the mixture was filtered through a sintered glass funnel and diluted withCH2Cl2. The round-bottom flask and AgI in the funnel were washed withCH2Cl2 and added to the rest of 0.185 the organic solution. This solution wastransferred to a separatory funnel and washed with distilled water(2 20 mL), saturated NaHSO3 solution (1 20 mL) and 10% NaHCO3solution (1 20 mL). The organic solution was dried over anhydrous Na2SO4,filtered and evaporated under vacuum. The crude mixture was purified bycolumn chromatography using silical gel and n-Hexane:AcOEt (7:3) mixture aseluent, furnishing our pure acetylated 2-iodoglycal with 50% yield for D-glucaland 56% yield for D-galactal.
32%	With N-iodo-succinimide; silver nitrate In acetonitrile at 80℃; for 3h; Inert atmosphere; Sealed tube;

	With N-iodo-succinimide; silver nitrate In acetonitrile at 70℃; Inert atmosphere;
	With N-iodo-succinimide; silver nitrate In acetonitrile at 80℃; Sealed tube; Inert atmosphere;	Starting Substrates General procedure: Compounds 2-iodo-3,4,6-tri-O-acetyl-D-glucal, 2-iodo-3,4,6-tri-O-benzyl-D-glucal, 2-iodo-3,4,6-tri-O-benzyl-D-galactal, 2-iodo-3,4-di-O-acetyl-L-rhamnal, 2-iodo-3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-D-glucal were prepared according to the literature:6,7m the corresponding glycal was dissolved in anhydrous acetonitrile (8 mL/mmol) under argon, and the resulting mixture was heated to 80 °C. At this temperature, N-iodosuccinimide (1.2 equiv)and silver nitrate (20 mol %) were added. The resulting mixture was stirred at 80 °C for 1-2 h. The mixture was filtrated on Celite with EtOAc, and concentrated with silica. The obtained crude material was purified on silica gel to furnish the corresponding 2-iodoglycal.

Reference： [1]Dharuman, Suresh; Vankar, Yashwant D. [Organic Letters, 2014, vol. 16, # 4, p. 1172 - 1175]
[2]Rojas; Lafuente; Echeverria; Piro; Vetere; Ponzinibbio [Tetrahedron Letters, 2020, vol. 61, # 36]
[3]Ferry, Angélique; Lubin-Germain, Nadège; Malinowski, Maciej; Van Tran, Thanh; de Robichon, Morgane [Advanced synthesis and catalysis, 2020]
[4]Darbem, Mariana P.; Esteves, Henrique A.; de Oliveira, Isadora M.; Stefani, Hélio A. [European Journal of Organic Chemistry, 2020, vol. 2020, # 32, p. 5220 - 5226]
[5]Ferry, Angélique; Lubin-Germain, Nadège; Malinowski, Maciej; Monasson, Olivier [Synthesis, 2021]

49
[ 3344-77-2 ]
[ 69226-51-3 ]
[ 4098-06-0 ]
12-bromododecyl 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxysulfonyl)amido-β-D-galactopyranoside [ No CAS ]