Name: 14131-84-1|(3aS,4S,6R,6aS)-6-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-ol|98%
Brand: Ambeed
SKU: A576241
Price: 5.0 USD
Availability: InStock
Rating: 94 (40 reviews)

1
[ 35023-80-4 ]
N,N-bis(2,3:5,6-di-O-isopropylidene-α-D-mannofuranosyl)hydroxylamine [ No CAS ]
[ 14131-84-1 ]

Yield	Reaction Conditions	Operation in experiment
1: 67% 2: 22%	With ethene; dimethyl formylphosphonate In chloroform at 70 - 75℃; for 22h; autoclave;

Reference： [1]Vasella, Andrea; Voeffray, Robert [Helvetica Chimica Acta, 1982, vol. 65, # 7, p. 1953 - 1964]

2
[ 530-26-7 ]
[ 67-64-1 ]
[ 14131-84-1 ]

Yield	Reaction Conditions	Operation in experiment
96%	With tetrapropylammonium tribromide at 20℃; for 2h; diastereoselective reaction;
94%	With iron(III) chloride
94%	With iron(III) chloride	2.2a Example 2a: Compound 2 was prepared by the procedure according to Okuda et al. [4]. (2) [a]D21 = 17.1 (c = 0.67, CH2CI2), MS (ESI): [M+Hf m/z Calcd for C12H2i06, 261.1 ; found, 261.0. H NMR, (400 MHz, CDCI3) δ = 1 -8HZ, d, 1 H, H1 '), 4.82 5.8HZ, JH3-.H4- = 3.8HZ, dd, 1 H, H3'), 4.63 Hz, d, 1 H, H2'), 4.42 (m, 1 H, H5'), 4.20 (JH4 IH.3' = 3.6Hz, Hz, dd, 1 H, Η4'), 4.08 (m, 2H, Η6'), 3.2 (s, 1 H, OH), 1.48 (3H, s, CHaCOCH2OCH3'), 1.47 (3H, s, CHaCOCH5OCH6'), 1 39 (3H, s, CH3COCH5OCH6 ), 1.34 (3H, s, CH3COCH2OCH3'). 3C NMR (400 MHz, CDCI3) δ 1 12.7 (C23O2C), 109.1 (C56'02C) 101.3 (C1 "), 85.5 (C2'), 80.1 (C4'), 79.4 (C3'), 73.1 (C5'), 66.5 (C6'), 26.8 (CH3COCH5OCH6'), 25.8 (CH3COCH2' ,OCH3"), 25.1 (CH3COCH5OCH6"), 24.4 (CH3COCH2' ,OCH3').

85%	With iodine at 25℃; for 2h;
51%	With iodine at 20℃; for 2h;	1 (3aS,4S,6R,6aS)-6-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-ol (6) Iodine (1.42 g, 5.6 mmol) was added to a suspension of d-mannose (5.0 g, 27.8 mmol) in acetone (250 mL) and the mixture was stirred for 2 h at ambient temperature. Then the reaction mixture was cooled down to 0 °C quenched with aqueous sodium bicarbonate and sodium thiosulfate. The mixture was extracted with CH2Cl2 (3x). The combined organic layers were dried (Na2SO4), filtered, and the solvent was removed in vacuo. The crude product was crystallized from an acetone/n-hexane mixture to give 6 as colorless solid (3.66 g, 14.1 mmol, 51%). Mp 125 °C; [α]D20 +16.1 (8.1; CH2Cl2); 1H NMR (CDCl3): δ [ppm]=1.32 (s, 3H, CH3), 1.38 (s, 3H, CH3), 1.45 (s, 3H, CH3), 1.46 (s, 3H, CH3), 2.92 (d, J=2.4 Hz, OH), 4.02-4.11 (m, 2H, OCHCH2O), 4.18 (dd, J=7.2/3.7 Hz, 1H, 6-H), 4.37-4.43 (m, 1H, OCHCH2O), 4.62 (d, J=5.9 Hz, 1H, 3a-H), 4.81 (dd, J=5.9/3.7 Hz, 1H, 6a-H), 5.38 (d, J=2.4 Hz, 4-H); 13C NMR (CDCl3): δ [ppm]=24.5 (1C, C(CH3)2), 25.3 (1C, C(CH3)2), 25.9 (1C, C(CH3)2), 27.1 (1C, C(CH3)2), 66.7 (1C, OCHCH2O), 73.4 (1C, OCHCH2O), 79.7 (1C, C-6a), 80.3 (1C, C-6), 85.5 (1C,C-3a), 101.3 (1C, C-4), 109.2 (1C, C(CH3)2), 112.8 (1C, C(CH3)2); IR (neat): ν [cm-1]=3436, 2978, 2948, 2899, 1372, 1201, 1060, 975, 838; HRMS (m/z): [M+Na]+ calcd for C12H20O6Na, 283.1152; found, 283.1152.
51%	With iodine at 20℃;
	With sulfuric acid at 23℃; for 12h;
	With sulfuric acid; potassium carbonate 1.) sonicated, 15 min, 2.) sonicated, 30 min; var. reagents,; Yield given. Multistep reaction;
	With phosphorus pentoxide for 25h; Yield given;
21.9 g	With iodine for 17h; Inert atmosphere; diastereoselective reaction;
	Stage #1: D-Mannose; acetone With copper(II) sulfate at 20℃; for 48h; Inert atmosphere; Stage #2: With sulfuric acid at 20℃; for 48h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Khan, Abu T.; Khan, Md. Musawwer; Adhikary, Anubendu [Carbohydrate Research, 2011, vol. 346, # 5, p. 673 - 677]
[2]Sauvageau, Janelle; Bhasin, Milan; Guo, Cynthia X.; Adekoya, Itunuoluwa A.; Gray-Owen, Scott D.; Oscarson, Stefan; Guazzelli, Lorenzo; Cox, Andrew [Carbohydrate Research, 2017, vol. 450, p. 38 - 43]
[3]Current Patent Assignee: NATIONAL UNIVERSITY OF IRELAND; NATIONAL REASEARCH COUNCIL OF CANADA - WO2018/205009, 2018, A1 Location in patent: Paragraph 0079
[4]Kim, Charles; Hoang, Richard; Theodorakis, Emmanuel A. [Organic Letters, 1999, vol. 1, # 8, p. 1295 - 1297]
[5]Jana, Sunit Kumar; Löppenberg, Marius; Daniliuc, Constantin G.; Jose, Joachim; Holl, Ralph [Tetrahedron, 2013, vol. 69, # 45, p. 9434 - 9442]
[6]Jana, Sunit Kumar; Löppenberg, Marius; Daniliuc, Constantin G.; Holl, Ralph [Tetrahedron, 2014, vol. 70, # 37, p. 6569 - 6577]
[7]Ghosh, Arun K.; McKee, Sean P.; Thompson, Wayne J. [Journal of Organic Chemistry, 1991, vol. 56, # 23, p. 6500 - 6503]
[8]Einhorn, Cathy; Luche, Jean-Louis [Carbohydrate Research, 1986, vol. 155, p. 258 - 261]
[9]Basha; Henry; McLaughlin; Ratajczyk; Wittenberger [Journal of Organic Chemistry, 1994, vol. 59, # 20, p. 6103 - 6106]
[10]Somarathne, Kalpani K.; McCone, Jordan A. J.; Brackovic, Amira; Rivera, José Luis Pinedo; Fulton, J. Robin; Russell, Euan; Field, Jessica J.; Orme, Christopher L.; Stirrat, Hedley L.; Riesterer, Jasmin; Teesdale-Spittle, Paul H.; Miller, John H.; Harvey, Joanne E. [Chemistry - An Asian Journal, 2019, vol. 14, # 8, p. 1230 - 1237]
[11]Li, Ming; Qiu, Yi-Feng; Wang, Cui-Tian; Li, Xue-Song; Wei, Wan-Xu; Wang, Yu-Zhao; Bao, Qiao-Fei; Ding, Ya-Nan; Shi, Wei-Yu; Liang, Yong-Min [Organic Letters, 2020, vol. 22, # 16, p. 6288 - 6293]

3
[ 3458-28-4 ]
[ 67-64-1 ]
[ 14131-84-1 ]

Yield	Reaction Conditions	Operation in experiment
87%	With toluene-4-sulfonic acid for 28h; Reflux;
85%	With iodine for 0.333333h; Heating;
85%	Stage #1: D-Mannose; acetone With iodine at 20℃; for 18h; Stage #2: With sodium thiosulfate In water Stage #3: With sodium hydrogencarbonate In water	Mannose protection: preparation of r2,3,5,61-di-O-isopropylidene-D-MannoseIn a three-necked flask were introduced 50.8 g of D-mannose (0.282 mol), 2.5 L of acetone and 14.3 g of iodine sublimate (56.4 mmol, 0.2 eq.). The medium was stirred at room temperature until solubilization of mannose was complete (about 18h). 640 ml of a 10% sodium thiosulfate aqueous solution were added. The pH value was brought back near to neutrality with a sodium hydrogenocarbonate saturated solution. After addition of the sodium chloride saturated solution, the organic phase was collected and extracted with chloroform. The combined organic phases were then dried on magnesium sulfate, filtered, and then evaporated. A yellow solid was produced, that was recristallized in a hexane/acetone mixture (80/20).-2) g) 3.2 1H NMR (400.13 MHz, CDCI3): ? 1 .34 (s, 3H, CH3), 1 .39 (s, 3H, CH3), 1 .47 (s, 3H, CH3),1 .48 (s, 3H, CH3), 3.45 (d, 1 H, 3JH-H = 2.4 Hz, OH), 4.08 (dd, 2H, 2JH-H = 5.5 Hz, 3JH-H = 1 .0 Hz, 6CH2), 4.19 (dd, 1 H, 3JH-H = 7.0 Hz, 3JH-H = 3.7 Hz, 4CH), 4.41 (q broad, 1 H, 3JH-H = 5.5 Hz, 5CH), 4.62 (d, 1 H, 3JN-H = 5.9 Hz, 2CH), 4.82 (dd, 2H, 3JH-H = 5.9 Hz, 3JH-H = 3.7 Hz, 3CH), 5.39 (d, 1 H,

82%	With phosphorus pentoxide for 12h; Inert atmosphere;
78%	With sulfuric acid; iodine for 6h; Reflux;
75%	With sulfuric acid at 20℃; for 4h; Inert atmosphere;	1 4.1.1 2,3:5,6-Di-O-isopropylidene-α-d-mannofuranose (1) Concd sulfuric acid (14 ml) was added to a solution of d-mannose (20 g, 0.11 mol) in anhydrous acetone (30 ml) and the mixture was stirred at rt for 4 h then neutralized with satd Na2CO3 solution. The reaction mixture was filtered and the filtrate was extracted using ethyl acetate (3 * 100 ml). The organic layers were evaporated and concentrated to dryness under reduced pressure gave 1 (21.6 g, 75%) as white crystals mp 121-122 °C. 1H NMR (300 MHz, CDCl3 δ 1.31 (s, 3H, CH3), 1.36 (s, 3H, CH3), 1.44 (s, 3H, CH3), 1.45 (s, 3H, CH3), 2.90 (br s, 1H), 4.05 (m, 2H), 4.16 (dd, J = 3.6, 7.1 Hz, 1H), 4.39 (ddd, J = 5.4, 5.5, 7.1 Hz, 1H), 4.59 (d, J = 5.9 Hz, 1H), 4.79 (dd, J = 3.6, 5.9 Hz, 1H), 5.36 (d, J = 3.6 Hz, 1H).
67%	Stage #1: D-Mannose; acetone With sulfuric acid at 20℃; for 12h; Stage #2: With sodium carbonate; pyrographite for 1h; Heating;
51%	With iodine at 20℃; for 2h;	1 4.2.1. (3aS,4S,6R,6aS)-6-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-ol (5) Iodine (1.42 g, 5.6 mmol) was added to a suspension of d-mannose (5.0 g, 27.8 mmol) in acetone (250 mL) and the mixture was stirred for 2 h at ambient temperature. Then the reaction mixture was cooled down to 0 °C quenched with aqueous sodium bicarbonate and sodium thiosulfate. The mixture was extracted with CH2Cl2 (3×). The combined organic layers were dried (Na2SO4), filtered, and the solvent was removed in vacuo. The crude product was crystallized from an acetone/n-hexane mixture to give 5 as colorless solid (3.66 g, 14.1 mmol, 51%). Mp: 125 °C; +16.1 (8.1; CH2Cl2); 1H NMR (CDCl3): δ (ppm) = 1.32 (s, 3H, CH3), 1.38 (s, 3H, CH3), 1.45 (s, 3H, CH3), 1.46 (s, 3H, CH3), 2.92 (d, J = 2.4 Hz, OH), 4.02-4.11 (m, 2H, OCHCH2O), 4.18 (dd, J = 7.2/3.7 Hz, 1H, 6-H), 4.37-4.43 (m, 1H, OCHCH2O), 4.62 (d, J = 5.9 Hz, 1H, 3a-H), 4.81 (dd, J = 5.9/3.7 Hz, 1H, 6a-H), 5.38 (d, J = 2.4 Hz, 4-H); 13C NMR (CDCl3): δ (ppm) = 24.5 (1C, C(CH3)2), 25.3 (1C, C(CH3)2), 25.9 (1C, C(CH3)2), 27.1 (1C, C(CH3)2), 66.7 (1C, OCHCH2O), 73.4 (1C, OCHCH2O), 79.7 (1C, C-6a), 80.3 (1C, C-6), 85.5 (1C, C-3a), 101.3 (1C, C-4), 109.2 (1C, C(CH3)2), 112.8 (1C, C(CH3)2); IR (neat): ν (cm-1) = 3436, 2978, 2948, 2899, 1372, 1201, 1060, 975, 838; HRMS (m/z): [M+Na]+ calcd for C12H20O6Na, 283.1152; found, 283.1152.
	With sulfuric acid In water at 20℃; for 1h;
	With iodine at 20℃; for 2h;
	With sulfuric acid

Reference： [1]Hassan, Firoj; Nasibullah, Malik; Ahmad, Naseem; Kamal, Azhar; Danish Rizvi, Syed Mohd; Khan, Mohd Sajid; Khan, Abdul Rahman [Oriental Journal of Chemistry, 2017, vol. 33, # 6, p. 2731 - 2741]
[2]Kartha, K.P.R. [Tetrahedron Letters, 1986, vol. 27, # 29, p. 3415 - 3416]
[3]Current Patent Assignee: UNIVERSITY OF MONTPELLIER - WO2009/4096, 2009, A1 Location in patent: Page/Page column 32-33
[4]Baldauf, Simon; Bode, Jeffrey W.; Boross, Gábor N.; Ogunkoya, Ayodele O. [Journal of Organic Chemistry, 2020]
[5]Lambu, Mallikharjuna Rao; Hussain, Altaf; Sharma, Deepak K.; Yousuf, Syed Khalid; Singh, Baldev; Tripathi, Anil. K.; Mukherjee, Debaraj [RSC Advances, 2014, vol. 4, # 22, p. 11023 - 11028]
[6]El-Nezhawy, Ahmed O.H.; Biuomy, Ayman R.; Hassan, Fatma S.; Ismaiel, Ayman K.; Omar, Hany A. [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 7, p. 1661 - 1670]
[7]Miner, Penny L.; Wagner, Timothy R.; Norris, Peter [Heterocycles, 2005, vol. 65, # 5, p. 1035 - 1049]
[8]Oddo, Alberto; Holl, Ralph [Carbohydrate Research, 2012, vol. 359, p. 59 - 64,6]
[9]Hachey, David L.; Parsons, W. Reed; McKay, Siripoom; Haymond, Morey W. [Analytical Chemistry, 1999, vol. 71, # 20, p. 4734 - 4739]
[10]Andrey, Olivier; Sperry, Jonathan; Larsen, Uffe S.; Brimble, Margaret A. [Tetrahedron, 2008, vol. 64, # 18, p. 3912 - 3927]
[11]Ali, Omar M.; Abdel-Rahman, Adel A.-H. [Monatshefte fur Chemie, 2008, vol. 139, # 1, p. 53 - 60]

4
[ 50-00-0 ]
[ 14131-84-1 ]
[ 91738-34-0 ]

Yield	Reaction Conditions	Operation in experiment
76%	With potassium carbonate In methanol; water at 85℃; for 48h;

Reference： [1]Witczak; Whistler; Daniel [Carbohydrate research, 1984, vol. 133, # 2, p. 235 - 245]

5
[ 16695-14-0 ]
[ 14131-84-1 ]
[ 34168-94-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	With piperidine In pyridine at 90℃;

Reference： [1]Aparicio, F. J. Lopez; Herrera, F. J. Lopez [Carbohydrate Research, 1980, vol. 80, p. C4 - C7]

6
[ 79265-30-8 ]
[ 14131-84-1 ]
2,3;5,6-di-O-isopropylidene-1-O-trimethylsilyl-α-D-mannofuranose [ No CAS ]

Reference： [1]Tetrahedron,1994,vol. 50,p. 3333 - 3348

7
[ 100-39-0 ]
[ 14131-84-1 ]
phenylmethyl 2,3:5,6-di-O-(1-methylethylidene)-α-D-mannofuranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium hydroxide In tetrahydrofuran for 0.25h; Ambient temperature;
90.3%	With potassium hydroxide; PEG-600 In tetrahydrofuran at 20℃;

Reference： [1]Bessodes; Shamsazar; Antonakis [Synthesis, 1988, # 7, p. 560 - 562]
[2]Chen, Fen-Er; Zhao, Jian-Feng; Xiong, Fang-Jun; Xie, Bin; Zhang, Ping [Carbohydrate Research, 2007, vol. 342, # 16, p. 2461 - 2464]

8
[ 528-76-7 ]
[ 14131-84-1 ]
[ 35880-41-2 ]

Yield	Reaction Conditions	Operation in experiment
91%	With triethylamine In dichloromethane at 0℃; for 0.0833333h;

Reference： [1]Fokt, Izabela; Szeja, Wieslaw [Carbohydrate Research, 1991, vol. 222, p. 271 - 276]

9
[ 106-49-0 ]
[ 14131-84-1 ]
[ 86266-41-3 ]

Yield	Reaction Conditions	Operation in experiment
87.5%	In ethanol for 3h; Heating;
65%	With magnesium sulfate In ethanol for 24h; Heating / reflux;	2,3: 5,6-Di-O-isopropylidene-?/-p-tolyl-D-mannosyl amineIn a 250 ml three-necked flask were introduced 15.1 g of protected D-mannose (58 mmol), 100 ml of ethanol, 15 g of magnesium sulfate and 12.2 g of freshly recristallized toluidine (181 mmol, 3 eq.). The medium was stirred at reflux for 24 hours. The reaction medium was cooled at room temperature whereby causing the precipitation of the expected protected sugar. The medium was filtered on sintered glass, the filtrate was introduced at 4C for 4 hours allowing the rest of the compound to precipitate. The whole solid was solubilized in dichloromethane, then filtered to remove magnesium sulfate. The filtrate was then evaporated under reduced pressure to produce a white solid. 3.26 1H RMN (400.13 MHz, CDCI3) : ? 1 .40 (s, 3H, CH3), 1 .44 (s, 3H, CH3), 1 .49 (s, 3H, CH3),1 .58 (s, 3H, CH3), 2.27 (s, 3H, CH3tol), 3.53 (dd, 1 H, 3JH-H = 3.3 Hz, 3JH-H = 8.5 Hz, 4CH), 4.12 (m, 2H, 6CH2), 4.47 (m, 1 H, 5CH), 4.71 (q, 1 H, 3JH-H = 6.0 Hz, 3JH-H = 3.2 Hz, 2CH), 4.82 (q, 1 H, 3JH-H = 6.0 Hz, 3JN-H = 3.2 Hz, 3CH), 4.91 (d, 1 H, 3JH-H = 10.0 Hz, NH), 5.03 (q, 1 H, 3JH-H = 10.0 Hz, 3JN-H = 3.2 Hz, 1CH), 6.72-7.01 (m, 4H, CHAr).

Reference： [1]Nifant'ev, E. E.; Rumyantseva, S. A.; Koroteev, M. P.; Sisneros, Ks.; Shashkov, A. S.; Kochetkov, N. K. [Journal of general chemistry of the USSR, 1983, vol. 53, # 1, p. 193 - 199][Zhurnal Obshchei Khimii, 1983, vol. 53, # 1, p. 221 - 228]
[2]Current Patent Assignee: UNIVERSITY OF MONTPELLIER - WO2009/4096, 2009, A1 Location in patent: Page/Page column 34-35

10
[ 98-88-4 ]
[ 14131-84-1 ]
[ 57526-34-8 ]

Yield	Reaction Conditions	Operation in experiment
96%	With pyridine In dichloromethane at 0℃; for 4h;
	With pyridine at 20℃; for 16h;

Reference： [1]Ravindranathan, T.; Hiremath, Shivajat V.; Reddy, D. Rajagopala; Rama Rao, A. V. [Carbohydrate Research, 1984, vol. 134, p. 332 - 336]
[2]Suhara, Yoshitomo; Ono, Keiichiro; Yoshida, Akihiro; Fujishima, Toshie; Saito, Nozomi; Honzawa, Shinobu; Kishimoto, Seishi; Sugiura, Takayuki; Waku, Keizo; Takayama, Hiroaki; Kittaka, Atsushi [Heterocycles, 2004, vol. 62, p. 423 - 436]

11
[ 7669-54-7 ]
[ 14131-84-1 ]
[ 139535-19-6 ]

Yield	Reaction Conditions	Operation in experiment
82%	With triethylamine In dichloromethane at 0℃; for 0.0833333h;

Reference： [1]Fokt, Izabela; Szeja, Wieslaw [Carbohydrate Research, 1991, vol. 222, p. 271 - 276]

12
[ 106-94-5 ]
[ 14131-84-1 ]
[ 118466-30-1 ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium hydroxide In tetrahydrofuran for 0.416667h; Ambient temperature;

Reference： [1]Bessodes; Shamsazar; Antonakis [Synthesis, 1988, # 7, p. 560 - 562]

13
[ 106-95-6 ]
[ 14131-84-1 ]
[ 54515-83-2 ]

Yield	Reaction Conditions	Operation in experiment
95%	With potassium hydroxide In tetrahydrofuran for 0.25h; Ambient temperature;
74%	With sodium hydride In N,N-dimethyl-formamide at 20℃; for 2h;
	With sodium hydride 1.) DMF, 0 deg C, 15 min, 2.) DMF, room temperature; Yield given. Multistep reaction;

Reference： [1]Bessodes; Shamsazar; Antonakis [Synthesis, 1988, # 7, p. 560 - 562]
[2]Mereyala, Hari Babu; Gurrala, Srinivas Reddy; Mohan, S. Krishna [Tetrahedron, 1999, vol. 55, # 37, p. 11331 - 11342]
[3]Mereyala, Hari Babu; Lingannagaru, Sarita Reddy [Tetrahedron, 1997, vol. 53, # 51, p. 17501 - 17512]

14
[ 53174-98-4 ]
[ 14131-84-1 ]
C₂₀H₂₄N₂O₆S [ No CAS ]

Reference： [1]Tetrahedron Letters,1994,vol. 35,p. 1011 - 1014

15
[ 14131-84-1 ]
[ 74-88-4 ]
[ 26255-73-2 ]

Yield	Reaction Conditions	Operation in experiment
95%	With potassium hydroxide In tetrahydrofuran for 0.5h; Ambient temperature;
92%	With sodium hydroxide; tetra-(n-butyl)ammonium iodide In dichloromethane for 24h; Ambient temperature;
87%	With sodium hydroxide; tetra-(n-butyl)ammonium iodide In dichloromethane at 20℃; for 24h;

Reference： [1]Bessodes; Shamsazar; Antonakis [Synthesis, 1988, # 7, p. 560 - 562]
[2]Veeneman; Gomes van Boom [Tetrahedron, 1989, vol. 45, # 23, p. 7433 - 7448]
[3]Kaliappan, Krishna P.; Subrahmanyam, Ayyagari V. [Organic Letters, 2007, vol. 9, # 6, p. 1121 - 1124]

16
[ 14131-84-1 ]
[ 17087-84-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	With n-butyllithium; chlorophosphoric acid diphenyl ester In tetrahydrofuran at 25℃; for 15h;
87.7%	With pyridine; thionyl chloride In chloroform for 4h; cooling;
87%	With pyridine; bis(trichloromethyl) carbonate In tetrahydrofuran at 0℃; for 4h;

83%	With pyridine; bis(trichloromethyl) carbonate In tetrahydrofuran at 25℃;
80%	With trichloroisocyanuric acid; triphenylphosphine In dichloromethane at 20℃; Inert atmosphere; Cooling; diastereoselective reaction;
78%	With tetrachloromethane; Hexamethylphosphorous triamide In tetrahydrofuran -78 deg C, 30 min.; room temp. 50 min;
	With thionyl chloride; thallium (I) ethoxide 1.) benzene, 15 min; 2.) benzene, 2 h; Yield given. Multistep reaction;
	With dmap; triethylamine; p-toluenesulfonyl chloride In dichloromethane at 25℃; for 2h;
4.3 g	With dmap; triethylamine; p-toluenesulfonyl chloride In dichloromethane at 20℃; for 3h;

Reference： [1]Hung, Shang-Cheng; Wong, Chi-Huey [Tetrahedron Letters, 1996, vol. 37, # 28, p. 4903 - 4906]
[2]Doboszewski, Bogdan [Journal of Carbohydrate Chemistry, 2002, vol. 21, # 1-2, p. 79 - 88]
[3]Miner, Penny L.; Wagner, Timothy R.; Norris, Peter [Heterocycles, 2005, vol. 65, # 5, p. 1035 - 1049]
[4]Cicchillo, Robert M.; Norris, Peter [Carbohydrate Research, 2000, vol. 328, # 3, p. 431 - 434]
[5]Somarathne, Kalpani K.; McCone, Jordan A. J.; Brackovic, Amira; Rivera, José Luis Pinedo; Fulton, J. Robin; Russell, Euan; Field, Jessica J.; Orme, Christopher L.; Stirrat, Hedley L.; Riesterer, Jasmin; Teesdale-Spittle, Paul H.; Miller, John H.; Harvey, Joanne E. [Chemistry - An Asian Journal, 2019, vol. 14, # 8, p. 1230 - 1237]
[6]Shing, Tony K. M.; Gillhouley, John G. [Tetrahedron, 1994, vol. 50, # 29, p. 8685 - 8698]
[7]Granata, Alessandro; Perlin, Arthur S. [Carbohydrate Research, 1980, vol. 86, p. 305 - 308]
[8]Kim, Charles; Hoang, Richard; Theodorakis, Emmanuel A. [Organic Letters, 1999, vol. 1, # 8, p. 1295 - 1297]
[9]Andrey, Olivier; Sperry, Jonathan; Larsen, Uffe S.; Brimble, Margaret A. [Tetrahedron, 2008, vol. 64, # 18, p. 3912 - 3927]

17
[ 14131-84-1 ]
[ 73014-56-9 ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris-(2-chloro-ethyl)-amine; triphenylphosphine; diethylazodicarboxylate In benzene for 0.5h; Heating;
56%	With 4-acetamidobenzenesulfonyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile for 12h; Reflux;	General procedure for reaction of sugar alcohols with p-ABSA and DBU The sugar (1.0 equivalent) and p-acetamidobenzenesulfonyl azide (2.0 equivalents) were dissolved in dry CH3CN (20 mL per gram of sugar). DBU (2.0 equivalents) was added to this mixture and the reaction was then refluxed for 12 hours. When reaction was complete, the solvent was evaporated under reduced pressure; the residue was dissolved in CH2Cl2 and washed three times with 5% aq. H2SO4 and twice with H2O. The organic layer was dried over anhydrous MgSO4, filtered, and then evaporated to dryness. The product was then purified by flash column chromatography using the indicated eluent.
	Multi-step reaction with 2 steps 1: 87 percent / triphosgene; pyridine / tetrahydrofuran / 4 h / 0 °C 2: 96 percent / NaN₃ / dimethylformamide / 12 h / 80 °C

Reference： [1]Schorkhuber; Zbiral [Liebigs Annalen der Chemie, 1980, vol. No.9, # 9, p. 1455 - 1469]
[2]Sacui, Iulia A.; Norris, Peter [Tetrahedron Letters, 2011, vol. 52, # 21, p. 2670 - 2672]
[3]Miner, Penny L.; Wagner, Timothy R.; Norris, Peter [Heterocycles, 2005, vol. 65, # 5, p. 1035 - 1049]

18
[ 14131-84-1 ]
2,3,5,6-di-O-isopropylidene-D-mannono-1,4-lactone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With Dess-Martin periodane; <i>tert</i>-butyl alcohol In dichloromethane at 25℃;
93%	With rhodium hydrido (PEt₃)3 complex; 1-Phenylbut-1-en-3-one In N,N-dimethyl-formamide at 40℃; for 4h;
91%	Stage #1: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose With oxalyl dichloride In dimethyl sulfoxide at -78℃; Stage #2: With triethylamine In dimethyl sulfoxide at 20℃;

91%	Stage #1: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose With oxalyl dichloride; dimethyl sulfoxide In dichloromethane at -78℃; Inert atmosphere; Stage #2: With triethylamine In dichloromethane at -78 - 20℃; Inert atmosphere;	2 4.2.2. (3aS,6R,6aS)-6-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-6,6a-dihydrofuro[3,4-d][1,3]dioxol-4(3aH)-one (6) Under N2 atmosphere a solution of oxalyl chloride (1.75 mL, 2.34 g, 18.4 mmol) in CH2Cl2 (50 mL) was cooled down to -78 °C. Then a solution of DMSO (2.91 mL, 3.2 g, 41.0 mmol) in CH2Cl2 (10 mL) was added dropwise and the mixture was stirred for 10 min at -78 °C. Then a solution of 5 (4.42 g, 17.0 mmol) in CH2Cl2 (25 mL) was added dropwise and the solution was stirred for another 30 min at -78 °C. Afterward, triethylamine (12 mL, 8.7 g, 86.3 mmol) was added and the mixture was allowed to warm to ambient temperature. Then n-hexane was added, the mixture was filtered, and the precipitate was washed with Et2O. The organic layer was concentrated in vacuo and the residue was purified by flash column chromatography (8 cm, 60 mL, n-hexane/ethyl acetate = 8/2, Rf = 0.19) to give 6 as colorless solid (4.0 g, 15.5 mmol, 91%). Mp: 126 °C; +56.5 (4.6; CH2Cl2); 1H NMR (CDCl3): δ (ppm) = 1.39 (s, 3H, CH3), 1.42 (s, 3H, CH3), 1.47 (s, 3H, CH3), 1.48 (s, 3H, CH3), 4.07 (dd, J = 9.3/3.7 Hz, 1 H, OCHCH2O), 4.15 (dd, J = 9.2/5.8 Hz, 1H, OCHCH2O), 4.37 (dd, J = 8.2/3.3 Hz, 1H, 6-H), 4.43 (ddd, J = 8.2/5.9/3.7 Hz, 1H, OCHCH2O), 4.84 (d, J = 5.3 Hz, 1H, 3a-H), 4.88 (dd, J = 5.3/3.4 Hz, 1H, 6a-H); 13C NMR (CDCl3): δ (ppm) = 25.2 (1C, C(CH3)2), 26.1 (1C, C(CH3)2), 26.9 (1C, C(CH3)2), 27.1 (1C, C(CH3)2), 66.6 (1C, OCHCH2O), 72.7 (1C, OCHCH2O), 75.9 (1C, C-6a), 76.2 (1C, C-3a), 78.2 (1C, C-6), 110.0 (1C, C(CH3)2), 114.7 (1C, C(CH3)2), 173.6 (1C, C-4); IR (neat): ν (cm-1) = 2987, 2891, 1769, 1381, 1194, 1082, 1039, 976, 851; HRMS (m/z): [M+Na]+ calcd for C12H18O6Na, 281.0996; found, 281.0993.
86%	With 3 A molecular sieve; pyridinium chlorochromate In dichloromethane for 24h; Ambient temperature;
85%	With acetic anhydride; dimethyl sulfoxide at 20℃; for 12h;
82%	With oxalyl dichloride; dimethyl sulfoxide; triethylamine In dichloromethane 1.) -60 deg C, 0.25 h; 2.) -60 deg C, 0.25 h;
81%	With air; acetic anhydride; dimethyl sulfoxide for 20h; Ambient temperature;
80%	With potassium carbonate In water at 20℃; electrolysis;
80%	With Collins oxidation agent In dichloromethane for 0.5h; Ambient temperature;
80%	With 4 A molecular sieve; pyridinium chlorochromate
52.3%	With ruthenium(III) chloride trihydrate; trichloroisocyanuric acid; tetrabutylammomium bromide; sodium acetate In water; acetonitrile at 25 - 45℃; Green chemistry; chemoselective reaction;
	With molecular sieve; pyridinium chlorochromate In dichloromethane

Reference： [1]Csuk, Rene; Doerr, Petra [Journal of Carbohydrate Chemistry, 1995, vol. 14, # 1, p. 35 - 44]
[2]Isaac, Isabelle; Stasik, Imane; Beaupere, Daniel; Uzan, Raoul [Tetrahedron Letters, 1995, vol. 36, # 3, p. 383 - 386]
[3]Jana, Sunit Kumar; Löppenberg, Marius; Daniliuc, Constantin G.; Holl, Ralph [Tetrahedron, 2014, vol. 70, # 37, p. 6569 - 6577]
[4]Oddo, Alberto; Holl, Ralph [Carbohydrate Research, 2012, vol. 359, p. 59 - 64,6]
[5]Shing, Tony K. M.; Gillhouley, John G. [Tetrahedron, 1994, vol. 50, # 29, p. 8685 - 8698]
[6]Lambu, Mallikharjuna Rao; Hussain, Altaf; Sharma, Deepak K.; Yousuf, Syed Khalid; Singh, Baldev; Tripathi, Anil. K.; Mukherjee, Debaraj [RSC Advances, 2014, vol. 4, # 22, p. 11023 - 11028]
[7]Buchanan; Smith; Wightman [Tetrahedron, 1984, vol. 40, # 1, p. 119 - 123]
[8]Moore; Cho; Casati; Kennedy; Reynolds; Mocek; Beale; Floss [Journal of the American Chemical Society, 1993, vol. 115, # 12, p. 5254 - 5266]
[9]Schaefer, Hans J.; Schneider, Roy [Tetrahedron, 1991, vol. 47, # 4-5, p. 715 - 724]
[10]Manna; McAnalley; Ammon [Carbohydrate Research, 1993, vol. 243, # 1, p. 11 - 27]
[11]Dondoni, Alessandro; Marra, Alberto; Rojo, Isabel; Scherrmann, Marie-Christine [Tetrahedron, 1996, vol. 52, # 9, p. 3057 - 3074]
[12]Yamaoka, Hidenori; Moriya, Narimasa; Ikunaka, Masaya [Organic Process Research and Development, 2004, vol. 8, # 6, p. 931 - 938]
[13]Orsini; Di Teodoro [Tetrahedron Asymmetry, 2002, vol. 13, # 12, p. 1307 - 1313] Orsini, Fulvia; Di Teodoro, Emanuela [Tetrahedron Asymmetry, 2003, vol. 14, # 17, p. 2521 - 2528]

19
[ 14131-84-1 ]
[ 35023-80-4 ]

Yield	Reaction Conditions	Operation in experiment
82%	With hydroxylamine hydrochloride; sodium acetate In ethanol at 65 - 70℃; for 1h;

Reference： [1]Basha; Henry; McLaughlin; Ratajczyk; Wittenberger [Journal of Organic Chemistry, 1994, vol. 59, # 20, p. 6103 - 6106]

20
[ 248590-47-8 ]
[ 14131-84-1 ]
25-(2,3:5,6-Di-O-isopropylidene-β-D-mannofuranosyl)oxy-26,27,28-trihydroxycalix[4]arene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With triphenylphosphine; diethylazodicarboxylate In toluene at 70℃; for 0.5h;
71%	With triphenylphosphine; diethylazodicarboxylate In toluene at 70℃; for 1h;

Reference： [1]Marra, Alberto; Scherrmann, Marie-Christine; Dondoni, Alessandro; Casnati, Alessandro; Minari, Patrizia; Ungaro, Rocco [Angewandte Chemie, 1994, vol. 106, # 23/24, p. 2533 - 2535]
[2]Dondoni, Alessandro; Marra, Alberto; Scherrmann, Marie-Christine; Casnati, Alessandro; Sansone, Francesco; Ungaro, Rocco [Chemistry - A European Journal, 1997, vol. 3, # 11, p. 1774 - 1782]

21
Carbonic acid allyl ester (3aS,4R,6R,6aS)-6-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-yl ester [ No CAS ]
[ 14131-84-1 ]

Yield	Reaction Conditions	Operation in experiment
85%	With palladium diacetate; sodium azide; trisodium tris(3-sulfophenyl)phosphine In water; acetonitrile at 25℃; for 1h;

Reference： [1]Sigismondi, Silvana; Sinou, Denis [Journal of Chemical Research - Part S, 1996, # 1, p. 46 - 47]

22
[ 75-89-8 ]
[ 14131-84-1 ]
(3aS,4R,6R,6aS)-4-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-6-(2,2,2-trifluoro-ethoxy)-tetrahydro-furo[3,4-d][1,3]dioxole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With triphenylphosphine; diethylazodicarboxylate In toluene at 20℃;

Reference： [1]Gueyrard, David; Rollin, Patrick; Nga, Truong Thi Thanh; Ourevitch, Michele; Begue, Jean-Pierre; Bonnet-Delpon, Daniele [Carbohydrate Research, 1999, vol. 318, # 1-4, p. 171 - 179]

23
[ 920-66-1 ]
[ 14131-84-1 ]
(3aS,4R,6S,6aS)-4-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-6-(2,2,2-trifluoro-1-trifluoromethyl-ethoxy)-tetrahydro-furo[3,4-d][1,3]dioxole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With triphenylphosphine; diethylazodicarboxylate In toluene at 20℃;

Reference： [1]Gueyrard, David; Rollin, Patrick; Nga, Truong Thi Thanh; Ourevitch, Michele; Begue, Jean-Pierre; Bonnet-Delpon, Daniele [Carbohydrate Research, 1999, vol. 318, # 1-4, p. 171 - 179]

24
[ 771-61-9 ]
[ 14131-84-1 ]
(3aS,4R,6S,6aS)-4-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-6-pentafluorophenyloxy-tetrahydro-furo[3,4-d][1,3]dioxole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With triphenylphosphine; diethylazodicarboxylate In toluene at 20℃;

Reference： [1]Gueyrard, David; Rollin, Patrick; Nga, Truong Thi Thanh; Ourevitch, Michele; Begue, Jean-Pierre; Bonnet-Delpon, Daniele [Carbohydrate Research, 1999, vol. 318, # 1-4, p. 171 - 179]

25
[ 75-03-6 ]
[ 14131-84-1 ]
[ 59122-84-8 ]

Yield	Reaction Conditions	Operation in experiment
76%	With silver(l) oxide In N,N-dimethyl-formamide at 20℃; for 24h;

Reference： [1]Abdel-Rahman, Adel A.-H.; El Ashry, El Sayed H.; Schmidt, Richard R. [Carbohydrate Research, 1999, vol. 315, # 1-2, p. 106 - 116]

26
(3aS,4R,6S,6aS)-4-(2,2-Dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-6-[((E)-propenyl)oxy]-tetrahydro-furo[3,4-d][1,3]dioxole [ No CAS ]
[ 14131-84-1 ]

Yield	Reaction Conditions	Operation in experiment
79%	With osmium(VIII) oxide; N-methyl-2-indolinone In acetone at 20℃; for 45h;

Reference： [1]Mereyala, Hari Babu; Gurrala, Srinivas Reddy; Mohan, S. Krishna [Tetrahedron, 1999, vol. 55, # 37, p. 11331 - 11342]

27
[ 250127-86-7 ]
[ 14131-84-1 ]

Yield	Reaction Conditions	Operation in experiment
88%	With osmium(VIII) oxide; N-methyl-2-indolinone In acetone at 20℃; for 12h;

Reference： [1]Mereyala, Hari Babu; Gurrala, Srinivas Reddy; Mohan, S. Krishna [Tetrahedron, 1999, vol. 55, # 37, p. 11331 - 11342]

28
[ 108-24-7 ]
[ 14131-84-1 ]
[ 14440-57-4 ]

Yield	Reaction Conditions	Operation in experiment
96%	With pyridine at 0 - 20℃; for 3h; Inert atmosphere;
	In ethyl acetate at 60℃; for 0.5h;
	With pyridine at -20 - 0℃; for 24h; Inert atmosphere;

Reference： [1]Li, Chao; Li, Luyang; Li, Yuxi; Shao, Feng; Tian, Xiaoying; Wang, Zheng [Angewandte Chemie - International Edition, 2022, vol. 61, # 1][Angew. Chem., 2022, vol. 134, # 1]
[2]Hachey, David L.; Parsons, W. Reed; McKay, Siripoom; Haymond, Morey W. [Analytical Chemistry, 1999, vol. 71, # 20, p. 4734 - 4739]
[3]Li, Ming; Qiu, Yi-Feng; Wang, Cui-Tian; Li, Xue-Song; Wei, Wan-Xu; Wang, Yu-Zhao; Bao, Qiao-Fei; Ding, Ya-Nan; Shi, Wei-Yu; Liang, Yong-Min [Organic Letters, 2020, vol. 22, # 16, p. 6288 - 6293]

29
[ 106-96-7 ]
[ 14131-84-1 ]
[ 250127-79-8 ]

Yield	Reaction Conditions	Operation in experiment
86%	With sodium hydroxide; tetra-(n-butyl)ammonium iodide In tetrahydrofuran at 20℃;
75%	Stage #1: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.5h; Stage #2: propargyl bromide In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 1h;	(3aS,4R,6S,6aS)-4-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-6-(prop-2-ynyloxy)tetrahydrofuro[3,4-d][1,3]dioxole (2) sodium hydride (60% in mineral oil, 0.64 g) was added to a stirred solution of 3 (3.6 g,13.84 mmol) in DMF (80 mL) at 0°C and allowed to stir for 30 min. This yellow mixture was cooled to 0°C and treated with propargyl bromide (4.2 g) in DMF (20 mL).The dark brown reaction mixture was allowed to stir foran hour at room temperature and quenched (at 5-10 °C)with saturated aqueous ammonium chloride (20 mL). The crude product was extracted with CH2Cl2 (3 × 30 mL),dried (Na2SO4) and concentrated. The residue was purifiedby column chromatography on silica gel (5% EtOAc :hexane) to afford 4 (3.1 g, 75%) as viscous oil. IR (KBr):ν 3312, 2997, 2929, 2266, 1632, 1377, 1222, 1162, 1074,1016 cm-1; 1H NMR (300 MHz, CDCl3): δ 5.52 (d, J = 3.7Hz, 1H, C1H), 4.59 (t, J = 3.9 Hz, 1H, C2H), 4.26 (dt, J =3.1, 7.3 Hz, 1H, C5H), 4.19 (s, 2H, CH2), 4.07-3.94 (m,3H, C4H, 2 × C6H), 3.65 (dd, J = 8.9, 4.1 Hz, 1H, C3H),3.16 (s,1H, CH), 1.53 (s, 3H, CH3), 1.40 (s, 3H, CH3),1.32 (s, 6H, 2 × CH3); 13C NMR (75 MHz, CDCl3): 112.5,109.4, 103.6, 80.1, 76.6, 75.2, 73.6, 65.2, 56.2, 25.6, 24.2.MS: m/z (M++Na) 321.
57%	With sodium hydride In N,N-dimethyl-formamide at 20℃; for 3h;

Reference： [1]Hausherr; Orschel; Scherer; Reissig [Synthesis, 2001, # 9, p. 1377 - 1385]
[2]Srinivas, Avula; Sunitha, Malladi; Raju, Kammachichu; Ravinder, Banothu; Anusha, Siluveru; Rajasri, Thallapalli; Swapna, Pothuganti; Sushmitha, Dupa; Swaroopa, Deva; Nikitha, Gurala; Govind Rao, Chakunta [Acta Chimica Slovenica, 2017, vol. 64, # 2, p. 319 - 331]
[3]Mereyala, Hari Babu; Gurrala, Srinivas Reddy; Mohan, S. Krishna [Tetrahedron, 1999, vol. 55, # 37, p. 11331 - 11342]

30
[ 14131-84-1 ]
[ 125181-25-1 ]

Yield	Reaction Conditions	Operation in experiment
98%	With 1H-imidazole; diphenylphosphinopolystyrene; iodine In dichloromethane at 20℃; for 2.5h;

Reference： [1]Caputo, Romualdo; Kunz, Horst; Mastroianni, Domenico; Palumbo, Giovanni; Pedatella, Silvana; Solla, Francesco [European Journal of Organic Chemistry, 1999, # 11, p. 3147 - 3150]

31
[ 1030268-24-6 ]
[ 14131-84-1 ]
3,6-anhydro-1,2:4,5-di-O-isopropylidene-D-glycero-D-manno-heptitol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 20℃; for 1h;

Reference： [1]Mereyala; Gadikota [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2000, vol. 39, # 3, p. 166 - 172]

32
[ 14131-84-1 ]
[ 3969-61-7 ]

Yield	Reaction Conditions	Operation in experiment
97%	With sodium tetrahydroborate In ethanol at 20℃;
91%	With lithium aluminium tetrahydride In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;	4.2.1 (R)-[(R)-2,2-Dimethyl-1,3-dioxolan-4-yl][(4S,5R)-5-(hydroxymethyl)-2,2-dimethyl-1,3-dioxolan-4-yl]methanol (18) Under N2 atmosphere, a 1M solution of 18 LiAlH4 in 74 THF (9.0mL, 9.0mmol) was added dropwise over 10min to a solution of 16 16 (3.1g, 12mmol) in THF (50mL) and the mixture was stirred for 3h at ambient temperature. Then the excess of LiAlH4 was carefully destroyed by adding a saturated aqueous solution 75 NH4Cl (30mL) and the formed precipitate was filtered off. Then the filtrate was extracted with ethyl acetate (3×). The combined organic layers were dried over sodium sulfate and concentrated in vacuo. The residue was purified by flash column chromatography (=6cm, h=15cm, V=50mL, cyclohexane/ethyl acetate=1/1, Rf=0.29) to give 19 18 (2.9g, 11mmol, 91%) as colorless oil. Specific rotation: [α]20D [α]D20 =-9.9 (c=4.4, CH2Cl2); 1H NMR (DMSO-d6): δ [ppm]=1.25 (s, 3H, C(CH3)2), 1.26 (s, 3H, C(CH3)2), 1.30 (s, 3H, C(CH3)2), 1.39 (s, 3H, C(CH3)2), 3.43-3.48 (m, 1H, CHOH), 3.63-3.73 (m, 2H, CH2OH), 3.80-3.86 (m, 1H, OCH2CHCHOH), 3.92-3.99 (m, 2H, OCH2CHCHOH (1H), OCH2CHCHOH), 4.13-4.20 (m, 2H, OCHCHCH2OH), 4.65 (d, J=6.8Hz, 1H, CHOH), 4.88-4.91 (m, 1H, CH2OH); 13C NMR (DMSO-d6): δ [ppm]=25.2 (1C, C(CH3)2), 25.4 (1C, C(CH3)2), 26.6 (1C, C(CH3)2), 26.7 (1C, C(CH3)2), 59.7 (1C, CH2OH), 66.5 (1C, OCH2), 69.3 (1C, CHOH), 75.7 (1C, OCH2CHCHOH), 75.8 (1C, OCHCHCH2OH), 77.4 (1C, OCHCHCH2OH), 107.2 (1C, C(CH3)2), 108.2 (1C, C(CH3)2); IR (neat): ν ν [cm-1]=3410, 2986, 2936, 2889, 1709, 1458, 1373, 1246, 1211, 1157, 1065, 1038, 918, 845, 795; HRMS (m/z): [M+H]+ calcd for C12H23O6: 263.1489, found: 263.1486.

Reference： [1]Shen, Xin; Wu, Yu-Lin; Wu, Yikang [Helvetica Chimica Acta, 2000, vol. 83, # 5, p. 943 - 953]
[2]Kalinin, Dmitrii V.; Agoglitta, Oriana; Van de Vyver, Hélène; Melesina, Jelena; Wagner, Stefan; Riemann, Burkhard; Schäfers, Michael; Sippl, Wolfgang; Löffler, Bettina; Holl, Ralph [Bioorganic and Medicinal Chemistry, 2019, vol. 27, # 10, p. 1997 - 2018]

33
[ 824-94-2 ]
[ 14131-84-1 ]
[ 164665-76-3 ]

Yield	Reaction Conditions	Operation in experiment
78%	With sodium hydride In N,N-dimethyl-formamide
78%	Stage #1: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.5h; Stage #2: p-methoxybenzyl chloride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1h;	2.2b Example 2b: Preparation of 4-methoxybenzyl 2,3,5,6-di-O-isopropylidene-a-D- mannofuranoside (3). To a solution of sodium hydride (60% in mineral oil, 5.23 g, 131 mmol) in anhydrous DMF (120 mL), was slowly added 2 (19.3 g, 74 mmol) in anhydrous DMF (60 mL) at 0°C. After 30 minutes, p-methoxybenzyl chloride (16.3 mL, 1 9.4 mmol) was injected dropwise and the mixture was stirred for 1 hour at 0°C after which the reaction was quenched by the addition of MeOH (15 mL). This mixture was stirred for 5 minutes and poured slowly into water. It was then extracted with ethyl acetate and the combined organic layers washed with water. The ethyl acetate fraction was then dried with magnesium sulfate, filtered and concentrated. Purification of the residue on silica gel chromatography afforded title compound 3 (22.2 g, 58 mmol, 78%). {Rf = 0.47, EtOAc/Hexanes, 3/7, v/v). [a)D21 = 68.0 (c = 0.63, CH2CI2), MS (ESI): [M+NH4]+ m/z Calcd for C20H32NO7, 398.2; found, 397.9. 1 H NMR, (400 MHz, CDCI3) δ 7.27 (JCHCCH2, cHcoMe = 9Hz, d, 2H, CHCCH2, PM = 9Hz, d, 2H, CHCOMe, PMB), 5.07 (s, 1 H, H1 '), 4.80 (JH3-,H2 d, 1 H , H3'), 4.65 (JH2',H3 = 6Hz, d, 1 H, H2'), 4.61 (JCHA, CHB = 1 1 HZ, ABX, 1 H, CHA, PMB), 4.43 (m, 2H, CHB, PMB and H5'), 4.15 (JmA, mB. = 8.5Hz, JHe-A.H5- = 6.3Hz, ABX, 1 H, Η6), 4.05 (JHe-B. new = 8.5Hz, JH6.B,H5' = 4.3Hz, ABX, 1 H, H6'B), 4.00 = 3.7Hz, JH4.,H5' = 7.8Hz, dd, 1 H, H4'), 3.82 (3H, s, CH30), 1.48 (6H, s, CHaCOCH2OCH3' and CH2COCH5OCH6'), (0213) I .42 (3H, s, 3C NMR (400 MHz, CDCI3) δ 159.4 (COMe), 129.8 (CHCCH2 PMB), 1 13.7 (CHCCH2 PMB), 1 12.7 (C2' ,3'02C), 109.5 (C5' ,6O2C) 105.2 (C1 '), 84.9 (C2'), 80.2 (C4'), 79.5 (C3'), 73.0 (C5"), 68.8 (CH2, PMB), 67.0 (C6'), 55.1 (OMe), 26.8 (CH3COCH5' ,OCH6'), 25.8 (CH3COCH2OCH3'), 25.0 (CH3COCH5OCH6-), 24.3 (CH3COCH2OCH3 ).

Reference： [1]Sauvageau, Janelle; Bhasin, Milan; Guo, Cynthia X.; Adekoya, Itunuoluwa A.; Gray-Owen, Scott D.; Oscarson, Stefan; Guazzelli, Lorenzo; Cox, Andrew [Carbohydrate Research, 2017, vol. 450, p. 38 - 43]
[2]Current Patent Assignee: NATIONAL UNIVERSITY OF IRELAND; NATIONAL REASEARCH COUNCIL OF CANADA - WO2018/205009, 2018, A1 Location in patent: Paragraph 0080

34
[ 814-68-6 ]
[ 14131-84-1 ]
[ 356797-33-6 ]

Yield	Reaction Conditions	Operation in experiment
81%	With triethylamine In dichloromethane at 20℃; for 10h;

Reference： [1]Radha Krishna, Palakodety; Kannan; Ilangovan; Sharma [Tetrahedron Asymmetry, 2001, vol. 12, # 6, p. 829 - 837]

35
[ 56506-90-2 ]
[ 14131-84-1 ]
[ 446044-30-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With zinc In 1,4-dioxane for 1.08333h; Heating;
90%	With zinc In 1,4-dioxane for 1h; Heating;

Reference： [1]Dolhem, Franck; Lièvre, Catherine; Demailly, Gilles [Tetrahedron Letters, 2002, vol. 43, # 10, p. 1847 - 1849]
[2]Dolhem, Franck; Lièvre, Catherine; Demailly, Gilles [Tetrahedron, 2003, vol. 59, # 2, p. 155 - 164]

36
[ 1779-49-3 ]
[ 14131-84-1 ]
[ 137945-76-7 ]

Yield	Reaction Conditions	Operation in experiment
87%	Stage #1: Methyltriphenylphosphonium bromide With lithium hexamethyldisilazane In tetrahydrofuran at 0℃; for 0.333333h; Inert atmosphere; Stage #2: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose In tetrahydrofuran at 0 - 20℃; for 2h; Inert atmosphere;
80%	In toluene for 0.25h; Heating;

Reference： [1]Liu, Yinxin; Liu, Jun; Zhao, Chuanfang; Du, Yuguo [Organic Letters, 2021, vol. 23, # 9, p. 3264 - 3268]
[2]Dolhem, Franck; Lièvre, Catherine; Demailly, Gilles [Tetrahedron, 2003, vol. 59, # 2, p. 155 - 164]

37
[ 155613-52-8 ]
[ 14131-84-1 ]
4-[6-(2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-yloxy]-3,5-dioxa-4-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With triethylamine In toluene for 16h;
44%	With triethylamine In toluene for 16h;

Reference： [1]Reetz, Manfred T.; Goossen, Lukas J.; Meiswinkel, Andreas; Paetzold, Jens; Jensen, Jakob Feldthusen [Organic Letters, 2003, vol. 5, # 17, p. 3099 - 3101]
[2]Reetz, Manfred T.; Goossen, Lukas J.; Meiswinkel, Andreas; Paetzold, Jens; Jensen, Jakob Feldthusen [Organic Letters, 2003, vol. 5, # 17, p. 3099 - 3101]

38
[ 14131-84-1 ]
[ 1026535-52-3 ]
9-fluorenyl 2:3,5:6-di-O-isopropylidene-α-D-mannofuranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 20℃;

Reference： [1]Ali, Ibrahim A. I.; El Ashry, El Sayed H.; Schmidt, Richard R. [European Journal of Organic Chemistry, 2003, # 21, p. 4121 - 4131]

39
[ 103-71-9 ]
[ 14131-84-1 ]
Phenyl-carbamic acid (3aS,4R,6R,6aS)-6-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-yl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose With sodium hydride In dichloromethane at 20℃; for 1h; Stage #2: phenyl isocyanate In dichloromethane for 0.5h;

Reference： [1]Knoben, Hans-Peter; Schlüter, Urs; Redlich, Hartmut [Carbohydrate Research, 2004, vol. 339, # 18, p. 2821 - 2833]

40
[ 1476-23-9 ]
[ 14131-84-1 ]
[ 150631-00-8 ]

Yield	Reaction Conditions	Operation in experiment
89%	Stage #1: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose With sodium hydride In dichloromethane at 20℃; for 1h; Stage #2: allylisocyanate In dichloromethane for 0.333333h;

Reference： [1]Knoben, Hans-Peter; Schlüter, Urs; Redlich, Hartmut [Carbohydrate Research, 2004, vol. 339, # 18, p. 2821 - 2833]

41
[ 109-90-0 ]
[ 14131-84-1 ]
Ethyl-carbamic acid (3aS,4R,6R,6aS)-6-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-yl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose With sodium hydride In dichloromethane at 20℃; for 1h; Stage #2: ethyl isocyanate In dichloromethane for 0.5h;

Reference： [1]Knoben, Hans-Peter; Schlüter, Urs; Redlich, Hartmut [Carbohydrate Research, 2004, vol. 339, # 18, p. 2821 - 2833]

42
[ 545-06-2 ]
[ 14131-84-1 ]
[ 83441-62-7 ]

Yield	Reaction Conditions	Operation in experiment
89%	With sodium hydride In dichloromethane at 20℃; for 1h;	2,3: Sj?-Di-O-isopropylidene-i-O-trichloroacetamidoyl-D-mannofuranose In a Schlenk tube that had been previously deoxygenated, under nitrogen atmosphere, were introduced 0.5 g of protected mannose (1.92 mmol), 15 ml of dichloromethane and 1 ml of trichloroacetonitrile (19.2 mmol, 10 eq.). 55 mg of sodium hydride (2.3 mmol, 1.2 eq.) were then added and the medium was stirred for one hour at room temperature.The reaction medium was then filtered on Celite. The obtained filtrate was evaporated under reduced pressure to produce a slightly coloured oil.This oil was then triturated in hexane thus resulting in a white precipitate. After the filtration, the filtration product was evaporated to produce a yellow oil that did spontaneously crystallize. Such solid corresponds to the pure trichloroacetamidate derivative. 3.53 1H NMR (400.13 MHz, (CD)3CO): ? 1 .39 (s, 3H, CH3), 1 .40 (s, 3H, CH3), 1 .47 (s, 3H,CH3), 1 .53 (s, 3H, CH3), 4.02 (AB, 2H, 6CH2), 4.22 (dd, 1 H, 3JH-H = 7.2 Hz, 3JH-H = 3.7 Hz, 4CH), 4.39 (q, 1 H, 5CH), 4.92 (d, 1 H, 3JH-H = 6.1 Hz, 2CH), 4.99 (dd, 1 H, 3JH-H = 5.9 Hz, 3JH-H = 3.3 Hz, 3CH), 6.31 (s, 1 H, 1CH), 8.61 (si, 1 H, NH).
73%	With sodium hydride In dichloromethane at 20℃; for 1h; Inert atmosphere;
66%	With potassium carbonate In dichloromethane at 20℃; for 24h;

Reference： [1]Current Patent Assignee: UNIVERSITY OF MONTPELLIER - WO2009/4096, 2009, A1 Location in patent: Page/Page column 36-37
[2]Khanam, Ariza; Mandal, Pintu Kumar [New Journal of Chemistry, 2021, vol. 45, # 34, p. 15386 - 15391]
[3]Hassan, Firoj; Nasibullah, Malik; Ahmad, Naseem; Kamal, Azhar; Danish Rizvi, Syed Mohd; Khan, Mohd Sajid; Khan, Abdul Rahman [Oriental Journal of Chemistry, 2017, vol. 33, # 6, p. 2731 - 2741]
[4]Ali, Ibrahim A. I.; Al-Masoudi, Iman A.; Saeed, Bahjat; Al-Masoudi, Najim A.; Colla, Palo La [Heteroatom Chemistry, 2005, vol. 16, # 2, p. 148 - 155]

43
[ 14131-84-1 ]
[ 54469-12-4 ]

Yield	Reaction Conditions	Operation in experiment
63%	With lithium nitrate; sodium carbonate; trifluoroacetic anhydride In acetonitrile at 0℃;

Reference： [1]Gavrila, Adina; Andersen, Lisbeth; Skrydstrup, Troels [Tetrahedron Letters, 2005, vol. 46, # 37, p. 6205 - 6207]

44
[ 14131-84-1 ]
[ 18107-18-1 ]
(R)-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-((4R,5S)-5-ethynyl-2,2-dimethyl-[1,3]dioxolan-4-yl)-methanol [ No CAS ]
(R)-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-((4R,5S)-2,2-dimethyl-5-trimethylsilanylethynyl-[1,3]dioxolan-4-yl)-methanol [ No CAS ]
[ 133634-82-9 ]

Yield	Reaction Conditions	Operation in experiment
1: 57% 2: 12% 3: 5%	Stage #1: diazomethyl-trimethyl-silane With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at 0℃; for 0.333333h; Stage #2: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose In tetrahydrofuran; hexane at -78 - 20℃; for 13h;

Reference： [1]Fuerstner, Alois; Wuchrer, Margarita [Chemistry - A European Journal, 2006, vol. 12, # 1, p. 76 - 89]

45
[ 37891-79-5 ]
[ 14131-84-1 ]
[ 197707-31-6 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose With sodium hydride In tetrahydrofuran at 0℃; for 2h; Stage #2: bis(methylsulfanyl)trimethylsilylmethane With n-butyllithium In tetrahydrofuran; hexane at 0 - 20℃;

Reference： [1]Kikelj, Vincent; Plantier-Royon, Richard; Portella, Charles [Synthesis, 2006, # 7, p. 1200 - 1204]

46
[ 105-65-7 ]
[ 14131-84-1 ]
O-isopropyl S-(2,3:-4,5-di-O-isopropylidene-α-D-mannofuranos-1-yl) dithiocarbonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With tributylphosphine; 4 A molecular sieve In toluene at 20℃; for 5h;

Reference： [1]Gueyrard, David; Tatibouët, Arnaud; Gareau, Yves; Rollin, Patrick [Organic Letters, 1999, vol. 1, # 3, p. 521 - 522]

47
[ 14131-84-1 ]
[ 5736-06-1 ]

Reference： [1]Tetrahedron,1991,vol. 47,p. 715 - 724

48
[ 105-39-5 ]
[ 14131-84-1 ]
[ 1078159-37-1 ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium hydride In N,N-dimethyl-formamide at 20℃; for 24h;

Reference： [1]Ali, Omar M.; Abdel-Rahman, Adel A.-H. [Monatshefte fur Chemie, 2008, vol. 139, # 1, p. 53 - 60]

49
[ 65600-74-0 ]
[ 14131-84-1 ]
4-(2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-2-oxo-2-diethoxymethyl-tetrahydro-6λ*5*-[1,3]dioxolo[4,5-d][1,2]oxaphosphinan-3-ol [ No CAS ]
4-(2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-2-oxo-2-diethoxymethyl-tetrahydro-6λ*5*-[1,3]dioxolo[4,5-d][1,2]oxaphosphinan-3-ol [ No CAS ]
4-(2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-2-oxo-2-diethoxymethyl-tetrahydro-6λ*5*-[1,3]dioxolo[4,5-d][1,2]oxaphosphinan-3-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		4-(2,2-Dimethyl-[1 ,3]dioxolan-4-yl)-2,2-dimethyl-2-oxo-2-diethoxymethyl-tetrahydro- 6?5-[1 ,3]dioxolo[4,5-d][1 ,2]oxaphosphinan-3-ol In a Schlenk tube that had been previously deoxygenated were introduced under nitrogen atmosphere 6.6 g of protected mannose (25.6 mmol), 5 g of ethyl diethoxyphosphinate (25.6 mmol, 1 eq.), 0.6 g of potassium tert-butoxide (5.2 mmol, 0.2 eq.) and 50 ml of anhydrous THF. This medium was then stirred at room temperature for 15 hours. To the medium were added 25 ml of a 0.1 N hydrochloric acid solution, 25 ml of a sodium chloride saturated solution. The thus obtained aqueous phase was extracted three times with chloroform. The organic phases were then combined, dried on magnesium sulfate, filtered, and then evaporated under reduced pressure to produce a coloured oil. This residue was then taken up in an ethyl acetate/n-hexane mixture, whereby causing the precipitation of major diastereomer. After filtration and evaporation of the filtrate, the residue obtained was purified on a silica gel column according to a DCM/ AcOEt gradient ranging from 100/0 to 80/20.), 3,19b 3.19 a, b et e Dia I (3,19a)1H NMR (400.13 MHz, CDCI3): ? 1 .25 (t, 3H, 3JH H = 6.9 Hz,, 9CH3), 1 .26 (t, 3H, 3JH H = 7.1 Hz,, "CH3), 1 .33 (s, 3H, CH3), 1 .36 (s, 3H, CH3), 1 .37 (s, 3H, CH3), 1 .54 (s, 3H, CH3), 3.78 (m, 4H, 8 10CH2), 4.06 (m, 2H, 6CH2), 4.13 (ddd, 1 H, 3JH-H = 1 .5 Hz, 3JH-H = 2.7 Hz, 3JH-H = 8.3 Hz, 3CH), 4.27 (Id, 1 H, 3JH-H = 3.3 Hz, 1CH), 4.31 (ddd, 1 H, 3JH-H = 4.1 Hz, 3JH-H = 5.8 Hz, 3JP_H = 9.8 Hz, 5CH), 4.53 (Id, 1 H, 3JH-H = 8.1 Hz, 4CH), 4.78 (d, 1 H, 2JP_H = 5.9 Hz, 7CH), 4.82 (ddd, 1 H, 3JH-H = 3.3 Hz, 3JN-H = 5.4 Hz, 3JP_H = 23.5 Hz, 2CH).MS HR+ (NBA): Theoretical mass 41 1 .1784; Experimental mass 41 1 .1790.Dia Il (3,19b)1H NMR (400.13 MHz, CDCI3): ? 1 .27 (t, 3H, 3JH-H = 7.1 Hz, 9CH3), 1 .28 (t, 3H, 3JH-H = 7.0 Hz, 11CH3), 1 .31 (s, 3H, CH3), 1 .34 (s, 3H, CH3), 1 .38 (s, 3H, CH3), 1 .52 (s, 3H, CH3), 3.82 (m, 4H, 8 10CH2), 4.1 1 (AB, 2H, 6CH2), 4.30 (AB, 2H, 1CH + 3CH), 4.47 (dd, 1 H, 3JP_H = 2,0 Hz, 3JH-H = 3.0 Hz, 4CH), 4.57 (Id, 1 H, 3JH-H = 7.8 Hz, 5CH), 4.81 (ddd, 1 H, 3JH-H = 3.0 Hz, 3JH-H = 7.8 Hz, 3JP_ H = 24.0 Hz, 2CH), 4.91 (d, 1 H, 2JP_H = 5.7 Hz, 7CH).

Reference： [1]Patent: WO2009/4096,2009,A1 .Location in patent: Page/Page column 46-47

50
[ 62-53-3 ]
[ 14131-84-1 ]
[ 1096142-86-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With magnesium sulfate In ethanol for 24h; Heating / reflux;	2,3: 5,6-Di-O-isopropylidene-?/-phenyl-D-mannosyl amineIn a 250 ml three-necked flask were introduced 15 g of protected D-mannose (58 mmol), 150 ml of ethanol, 15 g of magnesium sulfate and 16.5 ml of distilled aniline (181 mmol, 3 eq.). The medium was stirred at reflux for 24 hours.The medium was filtered on Celite, the obtained filtrate was evaporated under reduced pressure up to 30% of the initial volume. After a couple of hours at 40C, the expected product did precipitate. After a first filtration, petroleum ether was added to the filtrate so as to precipitate the rest.3.25 1H RMN (400.13 MHz, CDCI3) : ? 1 .31 (s, 3H, CH3), 1 .34 (s, 3H, CH3), 1 .39 (s, 3H, CH3),1 .48 (s, 3H, CH3), 3.46 (dd, 1 H, 3JH-H = 3.3 Hz, 3JH-H = 8.4 Hz, 4CH), 4.02 (m, 2H, 6CH2), 4.37 (qd, 1 H, 3JH-H = 4.5 Hz, 3JH-H = 5.7 Hz, 3JH-H = 8.6 Hz, 5CH), 4.63 (dd, 1 H, 2JH-H = 6.1 Hz, 3JH-H = 3.5 Hz, 2CH), 4.72 (dd, 1 H, 2JH-H = 6.1 Hz, 3JH-H = 3.3 Hz, 3CH), 4.93 (m, 2H, 1CH + NH), 6.72- 7.13 (m, 5H, CHAr).

Reference： [1]Current Patent Assignee: UNIVERSITY OF MONTPELLIER - WO2009/4096, 2009, A1 Location in patent: Page/Page column 34

51
[ 100-46-9 ]
[ 14131-84-1 ]
[ 1096142-84-5 ]

Yield	Reaction Conditions	Operation in experiment
58%	With magnesium sulfate In ethanol for 48h; Heating / reflux;	2,3: 5,6-Di-O-isopropylidene-?/-benzyl-D-mannosyl amineIn a three-necked flask were introduced 10 g of protected D-mannose (38 mmol), 100 ml of ethanol, 10 g of magnesium sulfate and 7.5 ml of distilled benzylamine (57 mmol, 1.5 eq.). The medium was stirred at reflux for 48 hours.The medium was filtered on Celite, the obtained filtrate was evaporated under reduced pressure. The oily residue was directly purified on a silica gel column using a dichloromethane/ethyl acetate system according to a gradient of from 100/0 to 50/50. The product was obtained as a yellow oil.3.24 1H NMR (400.13 MHz, CDCI3): ? 1 .19 (s, 3H, CH3), 1 .24 (s, 3H, CH3), 1 .30 (s, 3H, CH3),1 .38 (s, 3H, CH3), 3.30 (dd, 1 H, 3JH-H = 3.3 Hz, 3JH-H = 7.6 Hz, 4CH), 3.67 (dd, 1 H, 3JH-H = 5.9 Hz, 3JH-H = 7.2 Hz, 5CH), 3.81 (dd, 1 H, 2JH-H = 3.8 Hz, 3JH-H = 2,0 Hz, 2CH), 3.97 (m, 2H, 6CH2), 4.29 (td, 1 H, 3JN-H = 3.3 Hz, 3CH), 4.48 (ddd, 2H, 2JH-H = 41 .8 Hz, 3JH-H = 6.3 Hz, 2JH-H = 3.5 Hz, 7CH2), 4.66 (dd, 1 H, 3JH-H = 5.1 Hz, 3JH-H = 3.6 Hz, 1CH ), 4.81 (s, 1 H, NH), 1.22-1 Al (m, 5H, CHAr).

Reference： [1]Current Patent Assignee: UNIVERSITY OF MONTPELLIER - WO2009/4096, 2009, A1 Location in patent: Page/Page column 33

52
methyl phenylphosphinate [ No CAS ]
[ 14131-84-1 ]
(R_P,3R,4S,5R,6R,4'R)-3-hydroxy-4-(2.2-dimethyl[1.3]dioxolan-4-yl)-2.2-dimethyl-2-oxo-2-phenyltetrahydro-2λ⁵-[1.2]oxaphosphinane [ No CAS ]
[ 1096142-98-1 ]
[ 1096143-00-8 ]
[ 1096142-96-9 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 15h;	4-(2,2-Dimethyl-[1 ,3]dioxolan-4-yl)-2,2-dimethyl-2-oxo-2-phenyl-tetrahydro-6?5- [1 ,3]dioxolo[4,5-d][1 ,2]oxaphosphinan-3-olIn a Schlenk tube that had been previously deoxygenated were introduced under nitrogen atmosphere 30.25 g of [2,3-5,6]-di-O-isopropylidene-D-mannofuranose (0.1 16 mol), 2.4 g of potassium tert-butoxide (0.023 mol, 0.2 eq.) and 150 ml of anhydrous THF. 15 ml of methyl phenyl hydrogenophosphinate (0.1 16 mol, 1 eq.) were then added dropwise at room temperature under mechanical stirring. This medium was then stirred at room temperature for 15 hours.The reaction medium was filtered on sintered glass and the white precipitate obtained was rinsed with THF. The compound did correspond to the first pure diastereomer I (3.3a) (? = 31.4 ppm) (13.6 g). A sodium chloride saturated solution was then added to the filtrate. The aqueous phase thus obtained was extracted three times from dichloromethane. The organic phases were then combined, dried on magnesium sulfate, filtered, and then evaporated under reduced pressure to produce a coloured oil. This residue taken up in diethyl ether resulted in the selective precipitation of the diastereoisomer 3.3a that had been previously isolated. The filtration product was evaporated, and then purified by means of a silica gel flash chromatography. The eluent ether/AcOEt system (100/0-50/50) could isolate the three other impure diastereomers (3.3b, 3.3c and 3.3d) that were later easily purified by recrystallization in hexane. b, 3.3c 3.3 a, b, c et d Dia I 3.3a Yield = 35%1H NMR (400.13 MHz, CDCI3): ? 1 .41 (s, 3H, CH3), 1 .44 (s, 3H, CH3), 1 .47 (s, 3H, CH3),1 .71 (s, 3H, CH3), 3.25 (dd, 1 H, 3JH-H = 3.1 Hz, 2JH-H = 1 1 .7 Hz, OH), 4.04 (dd, 1 H, 3JH-H = 4.1 Hz, 3JH-H = 1 1 .7 Hz, 1CH), 4.13 (m, 1 H, 4CH), 4.17 (m, 2H, 6CH2), 4.47 (q, 1 H, 3JH-H = 5.5 Hz, 3JH-H = 12.1 Hz, 5CH), 4.65 (dd, 1 H, 3JH-H = 7.9 Hz, 3JH-H = 1 .3 Hz, 3CH), 4.84 (ddd, 1 H, 3JH-H = 4.1 Hz, 3JP-H = 24.6 Hz, 3JN-H = 7.9 Hz, 2CH), 7.50-7.86 (m, 5H CHAr).MS HR+ (NBA): Theoretical mass 384.1416; Experimental mass 384.1431 .Dia Il 3.3b Yield = 13% 1H NMR (400.13 MHz, CDCI3): ? 1 .38 (s, 3H, CH3), 1 .40 (s, 3H, CH3), 1 .43 (s, 3H, CH3),1 .57 (s, 3H, CH3), 4.14 (m, 2H, 6CH2), 4.26 (ddd, 1 H, 3JH-H = 1 .9 Hz, 2JH-H = 8.1 Hz, 3JP-H = 6.0 Hz, 4CH), 4.48 (m, 1 H, 5CH), 4.59 (dd, 1 H, 3JH-H = 3.5 Hz, 3JP-H = 13.7 Hz, 1CH), 4.64 (dd, 1 H, 3JH-H = 1 .3 Hz, 3JN-H = 7.6 Hz, 3CH), 4.88 (ddd, 1 H, 3JH-H = 7.6 Hz, 3JH-H = 3.5 Hz, 3JP-H = 26.8 Hz, 2CH), 7.49-7.73 (m, 5H CHAr). MS HR+ (NBA): Theoretical mass 384.1416; Experimental mass 384.1429.Dia III 3.3c Yield = 14%1H NMR (400.13 MHz, CDCI3): ? 1 .31 (s, 3H, CH3), 1 .33 (s, 3H, CH3), 1 .38 (s, 3H, CH3),1 .41 (s, 3H, CH3), 4.03 (m, 2H, 6CH2), 4.15 (dl, 1 H, OH), 4.30 (dd, 1 H, 3JH-H = 6.3 Hz, 3JP-H = 3.6 Hz, 1CH), 4.35 (m, 1 H, 5CH), 4.52 (m, 1 H, 4CH), 4.60 (td, 1 H, 3JH-H = 1 .7 Hz, 3JP.H = 7.2 Hz, 3CH), 4.88 (ddd, 1 H, 3JH-H = 3.6 Hz, 3JP.H = 24.5 Hz, 3JH-H = 7.2 Hz, 2CH), 7.38-7.89 (m, 5H, CHAr).MS HR+ (NBA): Theoretical mass 384.1416; Experimental mass 384.1402.[CC]D25 = + 50 (C = 0.1 9. MeOH)Dia IV, 3.3d Yield = 34%1H NMR (400.13 MHz, CDCI3): ? 1 .26 (s, 3H, CH3), 1 .31 (s, 3H, CH3), 1 .36 (s, 3H, CH3),1 .57 (s, 3H, CH3), 3.96 (qd, 1 H, 3JH-H = 1 .5 Hz, 2JH-H = 2.2 Hz, 2JH-H = 6,7 Hz, 4CH), 4.02 (m, 2H, 6CH2), 4.15 (dl, 1 H, 2JP-H = 3.6 Hz, 1CH), 4.34 (q, 1 H, 3JH-H = 6.1 Hz, 3JH-H = 1 1 .4 Hz, 5CH), 4.45 (ClL1 1 H, 3JN-H = 8.1 Hz, 3CH), 4.79 (ddd, 1 H, 3JH-H = 3.6 Hz, 3JP_H = 24.7 Hz, 3JH-H = 8.1 Hz, 2CH), 7.50-7.86 (m, 5H CHAr).MS HR+ (NBA): Theoretical mass 384.1416; Experimental mass 384.1415.[?]D25 = + 62 (c = 0.20, MeOH).

Reference： [1]Current Patent Assignee: UNIVERSITY OF MONTPELLIER - WO2009/4096, 2009, A1 Location in patent: Page/Page column 37-39

53
[ 65600-73-9 ]
[ 14131-84-1 ]
4-(2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-2-oxo-2-dimethoxymethyl-tetrahydro-6λ*5*-[1,3]dioxolo[4,5-d][1,2]oxaphosphinan-3-ol [ No CAS ]
4-(2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-2-oxo-2-dimethoxymethyl-tetrahydro-6λ*5*-[1,3]dioxolo[4,5-d][1,2]oxaphosphinan-3-ol [ No CAS ]
4-(2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2-dimethyl-2-oxo-2-dimethoxymethyl-tetrahydro-6λ*5*-[1,3]dioxolo[4,5-d][1,2]oxaphosphinan-3-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 15h;	4-(2,2-Dimethyl-[1 ,3]dioxolan-4-yl)-2,2-dimethyl-2-oxo-2-dimethoxymethyl-tetrahydro- 6?5-[1 ,3]dioxolo[4,5-d[1 ,2]oxaphosphinan-3-olIn a Schlenk tube that had been previously deoxygenated were introduced under nitrogen atmosphere 1.3 g of protected mannose (5.2 mmol), 0.8g of methyl dimethoxyphosphinate (5.2 mmol, 1 eq.), 120 mg of potassium tert-butoxide (1 mmol, 0.2 eq.) and 10 ml of anhydrous THF. This medium was then stirred at room temperature for 15 hours. To the medium were added 10 ml of a 0.1 N hydrochloric acid solution, 10 ml of a sodium chloride saturated solution. The thus obtained aqueous phase was extracted three times with chloroform. The organic phases were then combined, dryed on magnesium sulfate, filtered, and then evaporated under reduced pressure to produce a coloured oil. This residue was then purified using an automated flash chromatography (CH2CI2/Ac0Et eluent system using a gradient ranging from 100/0 to 0/100). %), 3.1? a, b et e Dia I (3.18a)1H NMR (400.13 MHz, CDCI3): ? 1 .34 (s, 3H, CH3), 1 .36 (s, 3H, CH3), 1 .39 (s, 3H, CH3), 1 .55 (s, 3H, CH3), 3.55 (s, 6H, 89CH3), 4.05 (m, 3H, 6CH2 + 3CH), 4.26 (ddd, 1 H, 3JH-H = 1 .5 Hz,3JH-H = 2.6 Hz, 2JP_H = 7.9 Hz, 1CH), 4.32 (dd, 1 H, 3JH-H = 3.5 Hz, 2JP_H = 5.9 Hz, 5CH), 4.54 (dd, 1 H, 3JN-H = 1 .6 Hz, 3JP-H = 7.9 Hz, 4CH), 4.66 (d, 1 H, 2JP-H = 5.9 Hz, 7CH), 4.85 (ddd, 1 H, 3JH-H = 3.4 Hz, 3JN-H = 7.9 Hz, 3JP.H = 23.7 Hz, 2CH).MS HR+ (NBA): Theoretical mass 382.3548; Experimental mass 382.3553.Dia Il (3.18b) 1H NMR (400.13 MHz, CDCI3): ? 1 .35 (s, 3H, CH3), 1 .39 (s, 3H, CH3), 1 .41 (s, 3H, CH3),1 .47 (s, 3H, CH3), 3.53 (s, 3H, 8CH), 3.56 (s, 3H, 9CH3), 3.84 (dd, 1 H, 3JH-H = 1 .8 Hz, 2JP.H = 10.5 Hz, 1CH), 4.09 (m, 2H, 6CH2), 4.32 (m, 1 H, 5CH), 4.46 (AB, 1 H, 4CH), 4.51 (ddd, 3JH-H = 1 .1 Hz, 3JH-H = 1 .5 Hz, 2JP-H = 7.3 Hz, 3CH), 4.74 (d, 1 H, 2JP-H = 1 1 .6 Hz, 7CH), 4.81 (ddd, 1 H, 3JH-H = 4.2 Hz, 3JN-H = 7.2 Hz, 2JP-H = 26.3 Hz, 2CH).Dia III1H NMR (400.13 MHz, CDCI3): ? 1.26 (s, 3H, CH3), 1 .29 (s, 3H, CH3), 1.37 (s, 3H, CH3), 1.53 (s, 3H, CH3), 3.49 (s, 3H, 8CH3), 3.57 (s, 3H, 9CH3), 4.12 (m, 3H, 1CH+ 6CH2), 4.39 (AB, 1 H, 5CH), 4.49 (ddd, 1 H, 3JH-H = 1.1 Hz, 3JH-H = 9.0 Hz, 2JP.H = 12.0 Hz, 4CH), 4.81 (ddd, 3JH-H = 1.9 Hz, 3JN-H = 2.3 Hz, 2JP.H = 9.8 Hz, 3CH), 4.84 (ddd, 1 H, 3JH-H = 2.8 Hz, 3JH-H = 7.3 Hz, 2JP.H = 26.2 Hz, 2CH), 5.08 (d, 1 H, 2JP-H = 15.3 Hz, 7CH).

Reference： [1]Current Patent Assignee: UNIVERSITY OF MONTPELLIER - WO2009/4096, 2009, A1 Location in patent: Page/Page column 45-46

54
[ 153413-65-1 ]
[ 14131-84-1 ]
C₂₄H₃₇N₂O₉P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 20℃; for 0.166667h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Dabkowski, Wojciech; Helinski, Jan; Kazimierczak, Lucja [ARKIVOC, 2010, vol. 2010, # 10, p. 350 - 357]

55
[ 103-82-2 ]
[ 14131-84-1 ]
[ 177562-09-3 ]

Yield	Reaction Conditions	Operation in experiment
90%	With dmap; dicyclohexyl-carbodiimide In dichloromethane; acetonitrile at 20℃; for 12h; Inert atmosphere;	1-O-(2-Phenylacetyl)-2,3;5,6-di-O-isopropylidene-α-D-mannofuranose (2) 2,3;5,6-Di-O-isopropylidene-α-D-mannofuranose (1, 3.05 g, 11.7 mmol), phenylacetic acid (1.76 g, 12.9 mmol), and 4-dimethylaminopyridine (0.233 g, 1.9 mmol) were added to a flame-dried round-bottom flask and dissolved in anhydrous CH2Cl2 (30 mL) and anhydrous CH3CN (30 mL). While stirring under nitrogen, a 1.0 M solution of 1,3-dicyclohexylcarbodiimide in CH2Cl2 (12.0 mL) was slowly added dropwise. The reaction mixture was then stirred overnight at RT resulting in a white precipitate; TLC showed the consumption of starting material. After gravity filtration the solvent was removed under reduced pressure and the resultant residue was dissolved in CH2Cl2. The solution was then washed with 5% H2SO4 (3 x 20 mL) followed by deionized H2O (2 x 20 mL). After drying with MgSO4, the filtrate was evaporated to give a solid residue which was recrystallized from ethanol to give 2 as colorless crystals (3.99 g, 90%); mp 70-74 °C; 1H NMR (CDCl3): δ 1.32 (s, 3H, CH3), 1.37 (s, 3H, CH3), 1.44 (s, 3H, CH3), 1.47 (s, 3H, CH3), 3.63 (s, 2H, CH2), 3.89 (dd, 1H, H-4, J = 3.7, 8.1 Hz), 3.96 (dd, 1H, H-6, J = 4.2, 8.6 Hz), 4.07 (dd, 1H, H-6’, J = 6.2, 8.4 Hz), 4.36 (ddd, 1H, H-5, J = 4.4, 6.0, 8.1 Hz), 4.66 (d, 1H, H-2, J = 5.5 Hz), 4.8 (dd, 1H, H-3, J = 3.5, 5.7 Hz), 6.13 (s, 1H, H-1), 7.2-7.4 (m, 5H, Ar-H); 13C NMR (CDCl3): δ 25.9, 26.4, 27.1, 28.3, 42.6, 68.0, 73.9, 80.4, 83.4, 86.0, 101.9, 110.4, 114.3, 128.3, 129.7 (double intensity), 130.2 (double intensity), 137.4, 170.8; MS: Calculated: 378.17 m/z, Found: (ESI pos) 401.2 m/z (M+Na+).

Reference： [1]Sacui, Iulia A.; Norris, Peter [Tetrahedron Letters, 2011, vol. 52, # 21, p. 2670 - 2672]

56
[ 177562-09-3 ]
[ 1309857-91-7 ]
[ 73014-56-9 ]
[ 14131-84-1 ]

Yield	Reaction Conditions	Operation in experiment
	With 4-acetamidobenzenesulfonyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane; acetonitrile at 20℃; for 12h;	Attempted diazo transfer to 2 using p-ABSA and DBU 1-O-(2-Phenylacetyl)-2,3;5,6-di-O-isopropylidene-α-D-mannofuranose (2, 0.378 g, 1.0 mmol) and p-acetamidobenzenesulfonyl azide (0.240 g, 1.0 mmol) were dissolved in dry CH2Cl2 (5 mL) and dry CH3CN (5 mL). While stirring at RT, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 1.1 eq.) was added dropwise over 2 h via syringe pump producing an orange solution. TLC showed the formation of three new spots as well as starting material in 3:1 hexanes - ethyl acetate. After stirring for 12 h the solvents were evaporated under reduced pressure. The resulting residue was dissolved in CH2Cl2 (20 mL) and washed with 5% H2SO4 (3 x 10 mL) followed by deionized H2O (2 x 10 mL). After drying the organic layers with MgSO4 the filtrate was evaporated to give a crude residue which was purified by flash column using 5:1 hexanes - ethyl acetate as eluent. Small amounts of diazo ester 3 were obtained as a yellow syrup; 1H NMR: δ 1.36 (s, 3H, CH3), 1.39 (s, 3H, CH3), 1.47 (s, 3H, CH3), 1.51 (s, 3H, CH3), 4.10 (m, 3H, H-4, H-6, H-6’), 4.43 (ddd, 1H, H-5, J = 4.4, 6.0, 7.8 Hz), 4.80 (d, 1H, H-2, J = 5.9 Hz), 4.90 (dd, 1H, H-3, J = 3.4, 6.0 Hz), 6.32 (s, 1H, H-1), 7.20-7.50 (m, 5H, Ar-H); 13C NMR: δ 26.0, 26.4, 27.2, 28.2, 68.0, 74.0, 80.5, 83.5, 86.2, 102.3, 110.4, 114.4, 125.1 (double intensity), 125.8, 127.2, 130.0 (double intensity), 164.2; IR absorption: 2095 cm-1 for diazo group. Additionally, small amounts of starting material 2, glycosyl azide 4, and lactol 1 were isolated as colorless syrups whose spectra matched authentic samples.

Reference： [1]Sacui, Iulia A.; Norris, Peter [Tetrahedron Letters, 2011, vol. 52, # 21, p. 2670 - 2672]

57
[ 100-39-0 ]
[ 14131-84-1 ]
[ 54469-08-8 ]
phenylmethyl 2,3:5,6-di-O-(1-methylethylidene)-α-D-mannofuranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: 2,3:5,6-di-O-isopropylidene-α-D-mannofuranose With sodium hydride In tetrahydrofuran at 0℃; for 0.666667h; Inert atmosphere; Stage #2: benzyl bromide In tetrahydrofuran at 20℃; Inert atmosphere;	2 4.1.2 Benzyl 2,3:5,6-di-O-isopropylidene-α-d-mannofuranose (2) To a solution of 2,3:5,6-di-O-isopropylidene-α-d-mannofuranose (11 g, 0.042 mmol) in THF (5 ml), a suspension of 60% NaH (0.24 g, 10 mmol) was added at 0 °C, and the mixture was stirred for 40 min. To the mixture, benzyl bromide (0.51 g, 3 mmol) was added and the reaction mixture was stirred overnight and concentrated by evaporation. A mixture of MeOH (30 ml) and water (100 ml) was added to the residue. The aqueous phase was extracted with EtOAc and dried (Na2SO4). The organic layer was concentrated under reduced pressure and the residue was purified by crystallization using ethyl acetate/hexane to provide 2α (12.7 g, 86%) as white crystals, mp 81-82 °C. 1H NMR (300 MHz, CDCl3 δ 1.34 (s, 3H, CH3), 1.42 (s, 3H, CH3), 1.50 (s, 3H, CH3), 1.51 (s, 3H, CH3), 3.93 (m, 1H), 4.18-4.47 (m, 3H), 4.50-4.65 (2d, J = 12.0 Hz, 2H, OCH2Ph), 4.75-4.88 (m, 2H), 5.11 (s, 1H, H-l), 7.26 (m, 5H, Ar).

Reference： [1]El-Nezhawy, Ahmed O.H.; Biuomy, Ayman R.; Hassan, Fatma S.; Ismaiel, Ayman K.; Omar, Hany A. [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 7, p. 1661 - 1670]

58
[ 14131-84-1 ]
[ 94898-41-6 ]

Yield	Reaction Conditions	Operation in experiment
95%	With diethylamino-sulfur trifluoride In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere;	2 (3aS,4R,6R,6aS)-4-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)-6-fluoro-2,2-dimethyl-tetrahydrofuro[3,4-d][1,3]dioxole (7) Under N2 atmosphere DAST (370 μL, 2.4 mmol) was added quickly to a solution of 6 (520 mg, 2.0 mmol) in dry tetrahydrofuran (20 mL) at room temperature. After 30 min, methanol (1.0 mL) was added. Then the solvent was evaporated and the crude product was purified by flash column chromatography (3 cm, 20 mL, cyclohexane/ethyl acetate=10:1, Rf=0.4) to give 7 as colorless oil (500 mg, 1.9 mmol, 95%). [α]D20 -9.3 (3.4, CH2Cl2); 1H NMR (CDCl3): δ [ppm]=1.34 (s, 3H, CH3), 1.38 (s, 3H, CH3), 1.45 (s, 3H, CH3), 1.46 (s, 3H, CH3), 4.06 (dd, J=8.8/4.4 Hz, 1H, OCHCH2O), 4.11 (dd, J=8.8/6.1 Hz, 1H, OCHCH2O), 4.16 (dd, J=7.6/3.5 Hz, 1H, 4-H), 4.38-4.42 (m, 1H, OCHCH2O), 4.76-4.86 (m, 1H, 6a-H), 4.85 (dd, J=5.7/3.5 Hz, 1H, 3a-H), 5.68 (d, J=59.4 Hz, 1H, 6-H); 13C NMR (CDCl3): δ [ppm]=24.7 (1C, C(CH3)2), 25.3 (1C, C(CH3)2), 26.0 (1C, C(CH3)2), 27.1 (1C, C(CH3)2), 66.8 (1C, OCHCH2O), 72.9 (1C, OCHCH2O), 78.7 (1C, C-3a), 82.8 (1C, C-4), 84.6 (d, 2JCF=41.5 Hz, 1C, C-6a), 109.5 (1C, C(CH3)2), 113.4 (1C, C(CH3)2), 113.8 (d, 1JCF=220.1 Hz, 1C, C-6); IR (neat): ν [cm-1]=2986, 2940, 1458, 1373, 1207, 1126, 1065, 964, 845; HRMS (m/z): [M+H]+ calcd for C12H20FO5 263.1289; found, 263.1284.

Reference： [1]Jana, Sunit Kumar; Löppenberg, Marius; Daniliuc, Constantin G.; Jose, Joachim; Holl, Ralph [Tetrahedron, 2013, vol. 69, # 45, p. 9434 - 9442]

59
[ 353244-61-8 ]
[ 14131-84-1 ]
(4R,6R)-6-((1R,2S,3R,4R)-1,2:4,5-di-O-isopropylidene-1,2,3,4,5-pentahydroxypentyl)-2,2-dimethyl-7-oxa-1-azabicyclo[2.2.1]heptane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
3.3 g	In toluene at 103℃; for 48h; Inert atmosphere; Sealed tube;	2 4.2 (4R,6R)-6-(1′R,2′S,3′R,4′R)-(1′,2′:4′,5′-Di-isopropylidene-1′,2′,3′,4′,5′-pentahydroxypentyl)-2,2-dimethyl-7-oxa-1-azabicyclo[2.2.1]heptane (14) A mixture of mercury(II) chloride (0.300 g, 1.105 mmol), THF (95 mL), water (1.28 mL), and aluminum foil (small pieces, 1.520 g, 56.338 mmol) was stirred at room temperature for 15 min, under an argon atmosphere. The mixture was cooled to 0 °C and 4-methyl-4-nitropent-1-ene 11 (3.700 g, 28.647 mmol) was added in portions. The reaction mixture was stirred at room temperature for 40 min, filtered through a Celite pad, and volatiles were distilled off. The crude 12 (3.000 g, 26.047 mmol) was dissolved in toluene (12 mL) and 2,3:5,6-di-O-isopropylidene-α-d-mannofuranose (4.210 g, 16.174 mmol) was added. The reaction mixture was deoxygenated and heated under an argon atmosphere at 103 °C for 2 days in a sealed tube and purified by column chromatography (hexane/ethyl acetate, 5:1, v/v) without a concentration to obtain 14 (3.300 g, 57%) as a white solid (mp 127-128 °C). Rf 0.51 (hexane/ethyl acetate, 3:1, v/v); [α]D20 -36 (c 0.23, CH2Cl2); νmax (KBr) 3564, 2988, 2964, 2940, 2888, 1640, 1464, 1376, 1256, 1069; δH (500 MHz, CDCl3) 4.81 (t(dd), 1H, 3J4,3exo=3J4,5exo 5.5, H-4), 4.47 (d, 1H, 3J2′,1′ 7.0, H-2′), 4.11 (dd, 1H, 3J1′,6 10.0, 3J1′,2′ 7.0, H-1′), 4.08-4.03 (m, 3H, H-4′, H-5′, H-5′′), 4.00-3.96 (m, 2H, H-3′, H-6), 2.17 (d, 1H, 3JOH,3′ 9.0, OH), 1.90 (dddd, 1H, 2J5exo,5endo 12.0, 3J5exo,4 5.5, 3J5exo,6 2.5 4J5exo,3exo 2.5, H-5exo), 1.78 (ddd, 1H, 2J3exo,3endo 11.5, 3J3exo,4 5.5, 4J3exo,5exo 2.5, H-3exo), 1.71 (dd, 1H, 2J5endo,5exo 12.0, 3J5endo,6 8.0, H-5endo), 1.25 (d, 1H, 2J3endo,3exo 11.5, H-3endo), 1.46, 1.43, 1.35, 1.34, 1.29, 1.21 [6×(s, 3H, CH3)]; δC (125 Hz, CDCl3) 109.3, 107.6 (2×-OC(CH3)2O-), 81.6 (C-4), 79.2 (C-1′), 76.6 (C-4′), 75.7 (C-2′), 69.3 (C-3′), 67.0 (C-5′), 66.2 (C-2), 59.5 (C-6), 47.0 (C-3), 37.6 (C-5), 31.4, 27.1, 26.8, 25.7, 24.6, 24.3 (6×CH3); HRMS m/z calcd for C18H32NO6 [M+H]+ 358.2230, found 358.2254.

Reference： [1]Mironiuk-Puchalska, Ewa; Rowicki, Tomasz; Sas, Wojciech; Koszytkowska-Stawińska, Mariola [Tetrahedron, 2013, vol. 69, # 46, p. 9826 - 9831]

60
[ 14131-84-1 ]
(3aS,6R,6aS)-6-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-3a-(hydroxymethyl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With formic acid; potassium carbonate In hexane; dichloromethane; water; ethyl acetate	I Step I: Step I: (3aS,6R,6aS)-6-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-3a-(hydroxymethyl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-ol To a suspension of (3aS,4S,6R,6aS)-6-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-ol (commercially available) (25.00 g, 96.1 mmol) and K2CO3 (19.92 g, 144.1 mmol) in MeOH (250.0 mL) is added formic acid (37% in water, 178.7 mL, 2.401 mmol). The reaction mixture is stirred 64 hrs at 95° C., cooled to 0° C., neutralized (pH 7) with aqueous H2SO4 (10%). The mixture is stirred 15 min at 0° C., at which point the resulting precipitate is filtered off and the mother liquor is concentrated in vacuo to provide a colorless oil. The crude oil is dissolved in CH2Cl2 and the organic phase is washed with water and brine. The solution is dried over Na2SO4, filtered, concentrated in vacuo and finally purified by flash column chromatography(220 g of silica) using 40-100% EtOAc/Hexane over 15 CV to afford the title compound (19.3 g, 66.5 mmol, 69%).

Reference： [1]Current Patent Assignee: VERTEX PHARMACEUTICALS (OLD) - US2014/274930, 2014, A1 Location in patent: Page/Page column

61
[ 100-46-9 ]
[ 14131-84-1 ]
[ 135902-07-7 ]

Yield	Reaction Conditions	Operation in experiment
58%	With magnesium sulfate In ethanol for 48h; Reflux;	b.3 b.3) Synthesis of 5,6-Di-O-isopropylidene-N-benzyl-D-mannosylamine 10 g of protected D-mannose ([2,3,5,6]-di-O-isopropylidene-D-mannose, described in patent application WO 2009/004096; 38 mmol), 100 ml of ethanol, 10 g of magnesium sulfate and 7.5 ml of distilled benzylamine (57 mmol, 1.5 eq.) are placed in a three-necked flask. The medium is stirred at reflux for 48 hours. The medium is filtered through Celite and the filtrate obtained is evaporated under reduced pressure. The oily residue is directly purified on a column of silica gel with a dichloromethane/ethyl acetate system in a gradient from 100/0 to 50/50. The product is obtained in the form of a yellow oil. Yld 58%. (0135) 1H NMR (400.13 MHz, CDCl3): δ 1.19 (s, 3H, CH3), 1.24 (s, 3H, CH3), 1.30 (s, 3H, CH3), 1.38 (s, 3H, CH3), 3.30 (dd, 1H, 3JH-H=3.3 Hz, 3JH-H=7.6 Hz, 4CH), 3.67 (dd, 1H, 3JH-H=5.9 Hz, 3JH-H=7.2 Hz, 5CH), 3.81 (dd, 1H, 2JH-H=3.8 Hz, 3JH-H=2.0 Hz, 2CH), 3.97 (m, 2H, 6CH2), 4.29 (td, 1H, 3JH-H=3.3 Hz, 3CH), 4.48 (ddd, 2H, 2JH-H=41.8 Hz, 3JH-H=6.3 Hz, 2JH-H=3.5 Hz, 7CH2), 4.66 (dd, 1H, 3JH-H=5.1 Hz, 3JH-H=3.6 Hz, 1CH), 4.81 (s, 1H, NH), 7.22-7.47 (m, 5H, CHAr).

Reference： [1]Current Patent Assignee: UNIVERSITY OF MONTPELLIER; UNIVERSITY OF PARIS SACLAY; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; PARIS 13 UNIVERSITY; ECOLE NATIONALE SUPERIEURE DE CHIMIE DE MONTPELLIER - US2015/376216, 2015, A1 Location in patent: Paragraph 0133; 0134; 0135

62
[ 905718-45-8 ]
[ 14131-84-1 ]
[ 62398-07-6 ]

Yield	Reaction Conditions	Operation in experiment
95%	With potassium <i>tert</i>-butylate In toluene at 20℃;

Reference： [1]Tolnai, Gergely L.; Nilsson, Ulf J.; Olofsson, Berit [Angewandte Chemie - International Edition, 2016, vol. 55, # 37, p. 11226 - 11230][Angew. Chem., 2016, vol. 128, # 37, p. 11392 - 11396]

63
[ 7294-51-1 ]
[ 14131-84-1 ]
[ 62398-06-5 ]

Yield	Reaction Conditions	Operation in experiment
62%	With copper diacetate; triethylamine In acetonitrile at 40℃; Sealed tube; stereoselective reaction;

Reference： [1]Dimakos, Victoria; Liu, Jacklyn J. W.; Ge, Zhenlu; Taylor, Mark S. [Organic and Biomolecular Chemistry, 2019, vol. 17, # 23, p. 5671 - 5674]

64
[ 3262-89-3 ]
[ 14131-84-1 ]
[ 54469-15-7 ]

Yield	Reaction Conditions	Operation in experiment
58%	With copper diacetate; triethylamine In acetonitrile at 40℃; Sealed tube; stereoselective reaction;

Reference： [1]Dimakos, Victoria; Liu, Jacklyn J. W.; Ge, Zhenlu; Taylor, Mark S. [Organic and Biomolecular Chemistry, 2019, vol. 17, # 23, p. 5671 - 5674]

65
[ 34907-38-5 ]
[ 14131-84-1 ]
3,5-dimethylphenyl-2,3:5,6-di-O-isopropylidene-α-D-mannofuranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With copper diacetate; triethylamine In acetonitrile at 40℃; Sealed tube; stereoselective reaction;

Reference： [1]Dimakos, Victoria; Liu, Jacklyn J. W.; Ge, Zhenlu; Taylor, Mark S. [Organic and Biomolecular Chemistry, 2019, vol. 17, # 23, p. 5671 - 5674]

66
[ 16396-62-6 ]
[ 14131-84-1 ]
4-vinylphenyl-2,3:5,6-di-O-isopropylidene-α-D-mannofuranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	With copper diacetate; triethylamine In acetonitrile at 40℃; Sealed tube; stereoselective reaction;

Reference： [1]Dimakos, Victoria; Liu, Jacklyn J. W.; Ge, Zhenlu; Taylor, Mark S. [Organic and Biomolecular Chemistry, 2019, vol. 17, # 23, p. 5671 - 5674]

67
[ 14131-84-1 ]
[ 159050-70-1 ]

Yield	Reaction Conditions	Operation in experiment
82%	With hydroxylamine hydrochloride; sodium hydrogencarbonate In ethanol; water at 60℃; for 1.66667h; Inert atmosphere;

Reference： [1]Baldauf, Simon; Bode, Jeffrey W.; Boross, Gábor N.; Ogunkoya, Ayodele O. [Journal of Organic Chemistry, 2020]

68
[ 19350-66-4 ]
[ 14131-84-1 ]
C₂₆H₃₇NO₁₁ [ No CAS ]
C₂₆H₃₇NO₁₁ [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2021,vol. 60,p. 9433 - 9438
Angew. Chem.,2021,vol. 133,p. 9519 - 9524,6

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
{[ item.p_purity ]}	{[ item.pr_size ]}	{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]}	{[ getRatePrice(item.pr_usd, 1,1) ]}	{[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]}	{[ item.pr_usastock ]}	Inquiry -	{[ item.pr_chinastock ]}	Inquiry -

CAS No. :	14131-84-1	MDL No. :	MFCD00134206
Formula :	C₁₂H₂₀O₆	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	-
M.W :	260.28	Pubchem ID :	-
Synonyms :

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P233-P260-P261-P264-P271-P280-P302+P352-P304-P304+P340-P305+P351+P338-P312-P321-P332+P313-P337+P313-P340-P362-P403-P403+P233-P405-P501	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 14131-84-1 ]

Quality Control of [ 14131-84-1 ]

Related Doc. of [ 14131-84-1 ]

Product Details of [ 14131-84-1 ]

Safety of [ 14131-84-1 ]

Application In Synthesis of [ 14131-84-1 ]

[ 14131-84-1 ] Synthesis Path-Upstream 1~1

[ 14131-84-1 ] Synthesis Path-Downstream 1~68

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry