[ CAS No. 1623-08-1 ]

Name: 1623-08-1|Dibenzyl hydrogen phosphate|98%
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Product Details of [ 1623-08-1 ]

CAS No. :	1623-08-1	MDL No. :	MFCD00004775
Formula :	C₁₄H₁₅O₄P	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	HDFFVHSMHLDSLO-UHFFFAOYSA-N
M.W :	278.24	Pubchem ID :	74189
Synonyms :

Safety of [ 1623-08-1 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313	UN#:	N/A
Hazard Statements:	H315-H319	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 1623-08-1 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 1623-08-1 ]
Downstream synthetic route of [ 1623-08-1 ]

[ 1623-08-1 ] Synthesis Path-Upstream 1~7

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[ 1623-08-1 ]
[ 50651-75-7 ]

Yield	Reaction Conditions	Operation in experiment
82.5%	With silver nitrate; sodium hydroxide In waterCooling with ice	[00250] Dibenzyl phosphate (2.78 g, 10 mmol) in water (40 ml_) was cooled in an ice bath. Subsequently, 1 N NaOH was added while shaking the flask until the pH of solution was about 7. The solid dissolved almost completely. Then silver nitrate (1 .89 g, 1 1 mmol) in water (20 ml_) was added slowly. After adding, the resulting solid was collected by filtration and washed with water. The solid was dried in vacuum over phosphorus pentoxide to yield silver dibenzyl phosphate (3.18 g) (yield, 82.5percent) as a white solid.

Reference： [1] Patent: WO2013/16668, 2013, A2, . Location in patent: Paragraph 00249; 00250

2
[ 1623-08-1 ]
[ 990-91-0 ]

Yield	Reaction Conditions	Operation in experiment
91%	With dicyclohexyl-carbodiimide In Isopropyl acetate at 3℃; for 0.916667 - 1.08333 h;	A 12 L round-bottomed flask was equipped with an overhead stirrer, thermocouple, N2 inlet, and an addition funnel. The vessel was charged with dibenzyl phosphate (762 g) and isopropyl acetate (3 L). The slurry was cooled to 3+/-3° C. and then the 1.08 M dicyclohexylcarbodiimide (DCC) solution (1.30 L) was added via the addition funnel while maintaining the batch temperature at 3+/-3° C. Typical addition times were between 25-35 minutes and the reaction was typically complete within 30 minutes. The cold slurry was filtered and the dicyclohexylurea waste cake was rinsed (agitated) with isopropyl acetate (3.x.600 mL). The filtrate and rinses were combined and concentrated in vacuo to a final volume of 1.5 L. The batch was transferred to a 12 round-bottomed flask that was equipped with an overhead stirrer, thermocouple, N2 inlet, and an addition funnel. The batch was diluted with heptane (500 mL) and seeded with 1 mol percent of tetrabenzyl pyrophosphate (8 g) to form a seed bed. Heptane (4.0 L) was then added to the stirred slurry at room temperature over 30 minutes. The batch was then cooled to 3+/-3° C. and aged for 1 hour. The slurry was filtered and the filter cake washed with 20percent isopropyl acetate/heptane (3.x.500 mL). The product cake was dried in vacuo and under a blanket of nitrogen overnight at room lemperature. Tetrabenzylpyrophosphate was isolated (671 g, 1.25 mol, after correcting for seed) as a white crystalline solid (91percent adjusted yield) which was stored in a freezer.
80%	at 0 - 5℃; for 0.5 h; Inert atmosphere	Under N2 protection, 7.6 g of dibenzyl phosphate and 30 ml of isopropyl acetate were added to a 250 ml dry three-necked flask. Stirring down to 0 ~ 5 . And then slowly dropping 1.1 M dicyclohexylcarbodiimide 13 ml. The dropping speed was controlled so that the temperature was always maintained at 0 to 5 ° C and the addition was completed in 30 minutes. Filter, remove DCU. The cake was washed with isopropyl acetate, the filtrate and the washings were combined and concentrated to 15 ml under reduced pressure. The mixture was diluted with 10 ml of heptane and then seeded. 40 ml of heptane was added while stirring, and the temperature of the mixture was kept at 0 to 5 ° C and crystallized for 1 hour. The cake was washed with a mixed solution of isopropyl acetate and heptane (1: 5) and dried in vacuo to give 5.7 g of a white solid in 80percent yield.
671 g	With dicyclohexyl-carbodiimide In Isopropyl acetate at 3℃; for 0.5 h; Inert atmosphere	Under a nitrogen atmosphere, dibenzyl phosphate (762 g) and isopropyl acetate (3 L) were added to a 12 L round bottom flask, and the slurryCooled to 3 ± 3 ° C and then added to the addition of 1. 08M dicyclohexylcarbodiimide (DCC) solution (1.30L) via an addition funnel whileThe bath temperature is maintained at 3 ± 3 ° C and the addition time is usually 25 to 35 minutes for about 30 minutes. After the reaction is over, it will coolThe slurry was filtered and the dicyclohexyl urea waste cake was washed with (isopropyl acetate) (3 * 600 ml) (stirred). Combine the filtrate and washPolyester solution, concentrated to a final volume of 1. 5L. The mixture was transferred to a 12 L round bottom flask and diluted with heptane (500 ml)And lmolpercent tetralyl pyrophosphate seed (8 g) was added to form a crystallographic bed. Then to 3 ± 3 ° C and aged for 1 hour. The slurry is overThe filter cake was washed with 20percent isopropyl acetate / heptane (3 * 500 ml) and the product cake was dried under vacuum at room temperature under vacuumovernight. The tetramethyl pyrophosphate (671 g, l. 25 mol) was isolated as a white solid which was frozen in a refrigerator.When R is a Q 4 alkyl group, a halogen atom, a cyano group or a nitro group in the compound structure of the formula 6, the preparation method is similar to that of the pyro-Acid tetrabenzyl ester (TBPP).

Reference： [1] Organic Syntheses, 2003, vol. 80, p. 219 - 226
[2] Carbohydrate Research, 2002, vol. 337, # 21-23, p. 1935 - 1940
[3] Patent: US2007/265442, 2007, A1, . Location in patent: Page/Page column 5
[4] Patent: CN102675369, 2017, B, . Location in patent: Paragraph 0049-0051
[5] Journal of the Chemical Society, 1953, p. 2257,2259
[6] Journal of the Chemical Society, 1951, p. 2267,2270
[7] Journal of the Chemical Society, 1952, p. 1234,1239
[8] Journal of the Chemical Society, 1953, p. 2257,2259
[9] Journal of the American Chemical Society, 1958, vol. 80, p. 6204,6206, 6212
[10] Journal of the Chemical Society, 1956, p. 1231,1235
[11] Journal of the Chemical Society, 1953, p. 2257,2259
[12] Angewandte Chemie, 1960, vol. 72, p. 236 - 249
[13] Tetrahedron, 1999, vol. 55, # 23, p. 7251 - 7270
[14] Patent: CN106146559, 2016, A, . Location in patent: Paragraph 0042; 0043

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[ 1623-08-1 ]
[ 98-59-9 ]
[ 71-43-2 ]
[ 990-91-0 ]

Reference： [1] Journal of the Chemical Society, 1952, p. 1234,1239

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[ 98-74-8 ]
[ 71-43-2 ]
[ 990-91-0 ]

Reference： [1] Journal of the Chemical Society, 1952, p. 1234,1239

5
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[ 121-44-8 ]
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[ 407-25-0 ]
[ 990-91-0 ]

Reference： [1] Journal of the Chemical Society, 1952, p. 1234,1239

6
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[ 1623-08-1 ]
[ 258516-84-6 ]

Yield	Reaction Conditions	Operation in experiment
74.1%	With sodium hydrogencarbonate; tetrabutylammonium sulfate In dichloromethane; water at 20℃; Cooling with ice	Step 1: Dibenzyl Chloromethyl Phosphate (33B) Dibenzyl phosphate (33A) (5.0 g, 0.018 mol) was dissolved into a mixture of dichloromethane (50 mL) and water (50 mL), then, tetrabutylammonium sulphate (1.22 g, 0.0036 mol) and sodium bicarbonate (6.0 g, 0.072 mol) was added under ice-water bath, followed by adding chloromethanesulfonyl chloride (2.97 g, 1.9 mL), and the mixture was stirred overnight at room temperature, stood and separated, and extracted with dichloromethane (50 mL). The combined organic extracts were washed with saturated brine (100 mL*2), dried over anhydrous sodium sulfate, concentrated under reduced pressure. The residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate (v/v)=5:1→3:1, gradient elution) to afford dibenzyl chloromethyl phosphate (33B) as a colorless liquid (4.35 g, yield: 74.1percent). ¹H NMR (400 MHz, CDCl₃): δ 7.36-7.26 (m, 10H), 5.63 (d, 2H), 5.10 (d, 4H).
74.1%	With tetra(n-butyl)ammonium hydrogensulfate; sodium hydrogencarbonate In dichloromethane; water at 20 - 30℃; Cooling with ice	Dibenzyl phosphate (33A) (5.0 g, 0.018 mol) was dissolved into a mixture of dichloromethane (50 mL) and water (50 mL), then,tetrabutylammonium sulphate (1.22 g, 0.0036 mol) and sodium bicarbonate (6.0 g, 0.072 mol) was added under icewaterbath, followed byadding chloromethanesulfonyl chloride (2.97 g, 1.9 mL), and the mixture was stirred overnight at room temperature, stood and separated, andextracted with dichloromethane (50 mL). The combined organic extracts were washed with saturated brine (100 mL×2), dried over anhydroussodium sulfate, concentrated under reduced pressure. The residue was purified by silica gel column chromatography (petroleum ether/ethylacetate (v/v)=5:1→3:1, gradient elution) to afford dibenzyl chloromethyl phosphate (33B) as a colorless liquid (4.35 g, yield: 74.1percent).

Reference： [1] Patent: US2016/60197, 2016, A1, . Location in patent: Paragraph 0362; 0363; 0364; 0365
[2] Patent: KR2016/5361, 2016, A, . Location in patent: Paragraph 1019; 1022; 1023-1025
[3] Journal of the American Chemical Society, 2011, vol. 133, # 31, p. 12021 - 12030

7
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[ 258516-84-6 ]

Yield	Reaction Conditions	Operation in experiment
48%	With tetrabutylammonium hydrogen sulfate; sodium hydrogencarbonate In dichloromethane; water at 0 - 20℃;	In one embodiment, another method of preparing the POM reagent dibenzyl(choloromethyl)phosphate, as shown in reaction Scheme 8 of FIG. 8. Briefly, dibenzylphosphate (10.6 g; 38.08 mmol) and chloromethyl sulfochloridate (7.52 g, 456.6 mmol/120 mL CH₂Cl₂) are dissolved in 320 mL water and 200 mL CH₂Cl₂with NaHCO₃(12.80 g, 152.32 mmol) and n-Bu₄NHSO₄(12.94 g, 38.08 mmol) at 0° C. to room temperature overnight, and then processed through a separation column with EA/H, EA. This reaction yields about 48percent of dibenzyl(choloromethyl)phosphate (6 g), which is confirmed with TLC as shown

Reference： [1] Tetrahedron Letters, 2002, vol. 43, # 21, p. 3793 - 3794
[2] Patent: JP2017/160205, 2017, A, . Location in patent: Page/Page column 135
[3] Patent: US2015/111858, 2015, A1, . Location in patent: Paragraph 0072

[ 1623-08-1 ] Synthesis Path-Downstream 1~69

1
[ 17176-77-1 ]
[ 1623-08-1 ]

Yield	Reaction Conditions	Operation in experiment
	With pyridine; Carbon tetrachloride; bromine
	With potassium permanganate; Sodium hydrogenocarbonate In 1,4-dioxane
	Multi-step reaction with 2 steps 1: tetrachloromethane; chlorine / <-15 2: tetrachloromethane; water

With potassium permanganate; Potassium bicarbonate In lithium hydroxide monohydrate at -3 - 3℃; for 5.5h; Large scale;

1.1.2; 5-8 , step purified dibenzyl phosphite and 15kg (about 95mol) potassium permanganate, 9kg (about 90mol) potassium bicarbonate,260kg of purified water, stirred and reacted at -33 for 5.5h,After TLC (thin layer chromatography) detected that the reaction was basically complete (the remaining amount of dibenzyl phosphite≤2.0wt%),Centrifuge or filter to remove the solid, add 120kg of ethyl acetate, stir for 15min, let stand,Separation, taking the water phase, adding 110kg of methylene chloride, 60kg of hydrochloric acid with a concentration of 4mol/L, stirring for 20min,Let stand, separate liquids, take the organic phase, extract the aqueous phase with dichloromethane (50kg×2) twice, combine the organic phases,Add 15kg of anhydrous sodium sulfate, stir, filter, and distill the filtrate under reduced pressure (vacuum degree≤-0.09MPa, temperature 4050°C) until basically no fraction is produced,Add 10kg of methyl tert-butyl ether, continue to distill under reduced pressure until no fraction is obtained, then add 15kg of methyl tert-butyl ether, and stir at 40 to 50 ° C for 20min,After that, the temperature was lowered to about 0 °C, stirred for 1 h, and centrifuged to obtain the wet product of dibenzyl phosphate (impurity content was about 2.5%);Further purification:The wet product of dibenzyl phosphate was added to 20.0 kg of methyl tert-butyl ether, stirred for 20 min, centrifuged, and dried by blasting (40-50 °C),Dibenzyl phosphate was obtained as a white powdery solid with a HPLC purity of 99.2% and a total yield of 74.5% (calculated as benzyl alcohol).Under the HPLC purity test, the retention time of the main peak of the test product (dibenzyl phosphate product) was basically the same as that of the standard product.

Reference： [1]Atherton; Howard; Todd [Journal of the Chemical Society, 1948, p. 1106,1111]
[2]Kluba,M. et al. [Roczniki Chemii, 1974, vol. 48, p. 277 - 286]
[3]Atherton; Openshaw; Todd [Journal of the Chemical Society, 1945, p. 382,384]
[4]- CN114380859, 2022, A Location in patent: Paragraph 0063-0065; 0070-0073; 0088-0095

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[ 1623-07-0 ]

Reference： [1]Journal of the Chemical Society,1956,p. 1371,1375

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[ 990-91-0 ]

Yield	Reaction Conditions	Operation in experiment
96%	With dicyclohexyl-carbodiimide In Isopropyl acetate at 0 - 6℃; for 1.5h; Inert atmosphere;
95%	With N,N-dicyclohexylurea In toluene at 20℃; for 5h;
91%	With dicyclohexyl-carbodiimide In Isopropyl acetate at 3℃; for 0.916667 - 1.08333h;	1 A 12 L round-bottomed flask was equipped with an overhead stirrer, thermocouple, N2 inlet, and an addition funnel. The vessel was charged with dibenzyl phosphate (762 g) and isopropyl acetate (3 L). The slurry was cooled to 3+/-3° C. and then the 1.08 M dicyclohexylcarbodiimide (DCC) solution (1.30 L) was added via the addition funnel while maintaining the batch temperature at 3+/-3° C. Typical addition times were between 25-35 minutes and the reaction was typically complete within 30 minutes. The cold slurry was filtered and the dicyclohexylurea waste cake was rinsed (agitated) with isopropyl acetate (3×600 mL). The filtrate and rinses were combined and concentrated in vacuo to a final volume of 1.5 L. The batch was transferred to a 12 round-bottomed flask that was equipped with an overhead stirrer, thermocouple, N2 inlet, and an addition funnel. The batch was diluted with heptane (500 mL) and seeded with 1 mol % of tetrabenzyl pyrophosphate (8 g) to form a seed bed. Heptane (4.0 L) was then added to the stirred slurry at room temperature over 30 minutes. The batch was then cooled to 3+/-3° C. and aged for 1 hour. The slurry was filtered and the filter cake washed with 20% isopropyl acetate/heptane (3×500 mL). The product cake was dried in vacuo and under a blanket of nitrogen overnight at room lemperature. Tetrabenzylpyrophosphate was isolated (671 g, 1.25 mol, after correcting for seed) as a white crystalline solid (91% adjusted yield) which was stored in a freezer.

80%	With Isopropyl acetate; dicyclohexyl-carbodiimide at 0 - 5℃; for 0.5h; Inert atmosphere;	6 Under N2 protection, 7.6 g of dibenzyl phosphate and 30 ml of isopropyl acetate were added to a 250 ml dry three-necked flask. Stirring down to 0 ~ 5 . And then slowly dropping 1.1 M dicyclohexylcarbodiimide 13 ml. The dropping speed was controlled so that the temperature was always maintained at 0 to 5 ° C and the addition was completed in 30 minutes. Filter, remove DCU. The cake was washed with isopropyl acetate, the filtrate and the washings were combined and concentrated to 15 ml under reduced pressure. The mixture was diluted with 10 ml of heptane and then seeded. 40 ml of heptane was added while stirring, and the temperature of the mixture was kept at 0 to 5 ° C and crystallized for 1 hour. The cake was washed with a mixed solution of isopropyl acetate and heptane (1: 5) and dried in vacuo to give 5.7 g of a white solid in 80% yield.
	With pyridine; dicyclohexyl-carbodiimide; benzene
	With thionyl chloride; benzene
	With triethylamine; acetonitrile
	With pyridine; acetonitrile
	With pyridine; chloroform
	With 2,6-dimethylpyridine; nitromethane; cyclopentanone-(<i>O</i>-benzenesulfonyl oxime )
	With pyridine; diethyl ether
	With dicyclohexyl-carbodiimide
250 mg	With dicyclohexyl-carbodiimide In diethyl ether; acetonitrile for 0.25h;
671 g	With dicyclohexyl-carbodiimide In Isopropyl acetate at 3℃; for 0.5h; Inert atmosphere;	1 Example 1 Preparation of tetrabenzyl pyrophosphate (TBPP) Under a nitrogen atmosphere, dibenzyl phosphate (762 g) and isopropyl acetate (3 L) were added to a 12 L round bottom flask, and the slurryCooled to 3 ± 3 ° C and then added to the addition of 1. 08M dicyclohexylcarbodiimide (DCC) solution (1.30L) via an addition funnel whileThe bath temperature is maintained at 3 ± 3 ° C and the addition time is usually 25 to 35 minutes for about 30 minutes. After the reaction is over, it will coolThe slurry was filtered and the dicyclohexyl urea waste cake was washed with (isopropyl acetate) (3 * 600 ml) (stirred). Combine the filtrate and washPolyester solution, concentrated to a final volume of 1. 5L. The mixture was transferred to a 12 L round bottom flask and diluted with heptane (500 ml)And lmol% tetralyl pyrophosphate seed (8 g) was added to form a crystallographic bed. Then to 3 ± 3 ° C and aged for 1 hour. The slurry is overThe filter cake was washed with 20% isopropyl acetate / heptane (3 * 500 ml) and the product cake was dried under vacuum at room temperature under vacuumovernight. The tetramethyl pyrophosphate (671 g, l. 25 mol) was isolated as a white solid which was frozen in a refrigerator.When R is a Q 4 alkyl group, a halogen atom, a cyano group or a nitro group in the compound structure of the formula 6, the preparation method is similar to that of the pyro-Acid tetrabenzyl ester (TBPP).

Reference： [1]Nelson, Todd D.; Rosen, Jonathan D.; Bhupathy; McNamara, James; Sowa, Michael J.; Rush, Chad; Crocker, Louis S.; Conway, Stuart J.; Holmes, Andrew B. [Organic Syntheses, 2003, vol. 80, p. 219 - 226]
[2]Elhalabi, Jordan; Rice, Kevin G. [Carbohydrate Research, 2002, vol. 337, # 21-23, p. 1935 - 1940]
[3]Current Patent Assignee: MERCK & CO INC - US2007/265442, 2007, A1 Location in patent: Page/Page column 5
[4]Current Patent Assignee: BEIJING HUAZHONG SIKANG PHARMACEUTICAL TECHNOLOGY - CN102675369, 2017, B Location in patent: Paragraph 0049-0051
[5]Khorana; Todd [Journal of the Chemical Society, 1953, p. 2257,2259]
[6]Mason; Todd [Journal of the Chemical Society, 1951, p. 2267,2270]
[7]Corby et al. [Journal of the Chemical Society, 1952, p. 1234,1239]
[8]Khorana; Todd [Journal of the Chemical Society, 1953, p. 2257,2259]
[9]Smith et al. [Journal of the American Chemical Society, 1958, vol. 80, p. 6204,6206, 6212]
[10]Kenner et al. [Journal of the Chemical Society, 1956, p. 1231,1235]
[11]Khorana; Todd [Journal of the Chemical Society, 1953, p. 2257,2259]
[12]Cramer,F. [Angewandte Chemie, 1960, vol. 72, p. 236 - 249]
[13]Vieira de Almeida, Mauro; Dubreuil, Didier; Cleophax, Jeannine; Verre-Sebrie, Catherine; Pipelier, Muriel; Prestat, Guillaume; Vass, Georges; Gero, Stephane D. [Tetrahedron, 1999, vol. 55, # 23, p. 7251 - 7270]
[14]Current Patent Assignee: BRIGHTGENE BIO MEDICAL TECHNOLOGY CO LTD - CN106146559, 2016, A Location in patent: Paragraph 0042; 0043

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[ 3240-34-4 ]
[ 1623-08-1 ]
[ 114197-83-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	for 0.00555556h; Microwave irradiation; neat (no solvent);
88%	With water In acetonitrile for 4h; Ambient temperature;
86%	for 0.0833333h; ground in mortar; Neat (no solvent);

Reference： [1]Location in patent: experimental part Zhou, Zhongshi; He, Xuehan [Journal of Chemical Research, 2009, # 1, p. 30 - 31]
[2]Koser, Gerald F.; Lodaya, Jayant S.; Ray, Dale G.; Kokil, Pandurang B. [Journal of the American Chemical Society, 1988, vol. 110, # 9, p. 2987 - 2988]
[3]Location in patent: experimental part Zhu, Min; Cai, Cheng Gang; Ke, Wei; Shao, Jing [Synthetic Communications, 2010, vol. 40, # 9, p. 1371 - 1376]

5
[ 1623-08-1 ]
[ 10378-06-0 ]
[ 147072-58-0 ]

Yield	Reaction Conditions	Operation in experiment
69%	In 1,2-dichloro-ethane for 24h; Inert atmosphere;
	In benzene Ambient temperature;

Reference： [1]Bernardes, Gonalo J. L.; Kikkeri, Raghavendra; Maglinao, Maha; Laurino, Paola; Collot, Mayeul; Hong, Sung You; Lepenies, Bernd; Seeberger, Peter H. [Organic and Biomolecular Chemistry, 2010, vol. 8, # 21, p. 4987 - 4996]
[2]Yamazaki, Tatsumi; Warren, Christopher D.; Herscovics, Annette; Jeanloz, Roger W. [Canadian Journal of Chemistry, 1981, vol. 59, p. 2247 - 2252]

6
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[ 39824-26-5 ]
Phosphoric acid dibenzyl ester (3aR,4R,6R,6aR)-6-(6-chloro-purin-9-yl)-2,2-dimethyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-ylmethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With triphenylphosphine; diethylazodicarboxylate In pyridine Ambient temperature;

Reference： [1]Saady; Lebeau; Mioskowski [Tetrahedron Letters, 1995, vol. 36, # 13, p. 2239 - 2242]

7
[ 1623-08-1 ]
[ 538-37-4 ]

Yield	Reaction Conditions	Operation in experiment
	With sulfuryl dichloride In tetrachloromethane at 25℃; for 0.25h;
	With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide for 1h;
	With N-chloro-succinimide In benzene at 20℃; for 1h;

	With oxalyl dichloride In dichloromethane at 20℃; for 1h;	6.4.4 A solution of dibenzyl phosphate (3.76g, 13.5 mmol) in CH2Cl2 (10 mL) ^r as, treated with oxalyl chloride (1.17, 13.5 mmol) and DMF (0.5 mL). The mixture was stirred at room temperature for Ih, the solvent was removed by rotary evaporation and the residue was dried in vacuo for 2h to afford dibenzyl chlorophosphate as a yellowish solid. The residme was suspended in CH2Cl2 (5 mL), cooled to 0 0C, treated with a solution of benzylic alcohol M (1.7g, 6.7 mmol) in CH2Cl2 (5 mL) then DBU (2.02 mL, 13.5 mmol, added dropwlse). The mixture was stirred at room temperature for lh30, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography over silica gel using a gradient of 0-10% EtOAc/hexane as eluent.Yield: 1.3g, 40%. 1H NMR (300 MHz, CDCl3): δ (ppm) -0.01 (s, 6H); 0.83 (s, 9H); 4.65 (s, 2H); 4.87-4.96 Cd, 4H); 4.96-5.06 (d, 2H); 7.07-7.41 (m, 14H).
	With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere;
	With oxalyl dichloride In dichloromethane at 20℃; for 1h;	4; 6.6.4.4 A solution of dibenzyl phosphate (3.76 g, 13.5 mmol) in CH2Cl2 (10 mL) was treated with oxalyl chloride (1.17, 13.5 mmol) and DMF (0.5 mL). The mixture was stirred at room temperature for 1 h, the solvent was removed by rotary evaporation and the residue was dried in vacuo for 2 h to afford dibenzyl chlorophosphate as a yellowish solid. The residue was suspended in CH2Cl2 (5 mL), cooled to 0° C., treated with a solution of benzylic alcohol M (1.7 g, 6.7 mmol) in CH2Cl2 (5 mL) then DBU (2.02 mL, 13.5 mmol, added dropwise). The mixture was stirred at room temperature for 1 h30, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography over silica gel using a gradient of 0-10% EtOAc/hexane as eluent. Yield: 1.3 g, 40%. 1H NMR (300 MHz, CDCl3): δ (ppm) -0.01 (s, 6H); 0.83 (s, 9H); 4.65 (s, 2H); 4.87-4.96 (d, 4H); 4.96-5.06 (d, 2H); 7.07-7.41 (m, 14H).
	With oxalyl dichloride In dichloromethane at 0 - 20℃;	58 stirred solution of bis(phenylmethyl) hydrogen phosphate (15 g, 54 mmol) and DMF (0.150 ml, 1.94 mmol) in anhydrous dichloromethane (160 ml), was cooled to 0 0C. To the solution was added oxalyl chloride (9.44 ml_, 108 mmol) dropwise. The reaction mixture stirred at ambient temperature for 1.5 h. The solvents were evaporated in vacuo. The residue was diluted with toluene (100 ml) and evaporated in vacuo to give bis(phenylmethyl) chloridophosphate (17.12 g) as a pale orange liquid.
	With sulfuryl dichloride In toluene at 25℃; for 0.5h; Inert atmosphere;	1 Preparation of dibenzylphosphoryl chloride In 100ml three bottles, assembly thermometer, magnetic stirring, N2. Under N2, 10 g (36 mmol) of dibenzyl phosphate and 25 ml of toluene were added to the flask. The temperature of the reaction mixture was controlled to 25 ° C or lower, and 3.6 ml (43 mmol) of sulfonyl chloride was slowly added dropwise. After all the additions, keep the temperature and continue stirring for 30 minutes. The reaction solution was transferred to a 100 ml dry one-necked flask, and the solvent was distilled off under reduced pressure. The residue was further added to 10 ml of toluene and evaporated under reduced pressure. The procedure was repeated three times to ensure that the residue did not contain sulfonyl chloride. The residue was dissolved in 5 ml of tetrahydrofuran and used directly in the next step.
	With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 1h;	4.4 A solution of dibenzyl phosphate (3.76g, 13.5 mmol) in CH2C12 (10 mL) was treated with oxalyl chloride (1.17, 13.5 mmol) and DMF (0.5 mL). The mixture was stirred at room temperature for lh, the solvent was removed by rotary evaporation and the residue was dried in vacuo for 2h to afford dibenzyl chlorophosphate as a yellowish solid. The residue was suspended in CHSCIS (5 mL), cooled to 0 °C, treated with a solution of benzylic alcohol M (1.7g, 6.7 mmol) in CH2C12 (5 mL) then DBU (2.02 mL, 13.5 mmol, added dropwise). The mixture was stirred at room temperature for LH30, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography over silica gel using a gradient of 0-10% EtOAc/hexane as eluent.
	With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; for 1.5h;

Reference： [1]Boger, Dale L.; Haynes, Nancy-Ellen; Warren, Mark S.; Ramcharan, Joseph; Kitos, Paul A.; Benkovic, Stephen J. [Bioorganic and Medicinal Chemistry, 1997, vol. 5, # 9, p. 1853 - 1857]
[2]Vincent, Stéphane P; Gastinel, Louis N [Carbohydrate Research, 2002, vol. 337, # 11, p. 1039 - 1042]
[3]Itoh, Kenji; Huang, Zhishu; Liu, Hung-Wen [Organic Letters, 2007, vol. 9, # 5, p. 879 - 882]
[4]Current Patent Assignee: TEVA PHARMACEUTICAL INDUSTRIES LTD. - WO2006/89397, 2006, A1 Location in patent: Page/Page column 114
[5]Dykhuizen, Emily C.; Kiessling, Laura L. [Organic Letters, 2009, vol. 11, # 1, p. 193 - 196]
[6]Current Patent Assignee: TEVA PHARMACEUTICAL INDUSTRIES LTD. - US2005/267073, 2005, A1 Location in patent: Page/Page column 50
[7]Current Patent Assignee: GLAXOSMITHKLINE PLC - WO2010/122089, 2010, A1 Location in patent: Page/Page column 77
[8]Current Patent Assignee: BEIJING HUAZHONG SIKANG PHARMACEUTICAL TECHNOLOGY - CN102675369, 2017, B Location in patent: Paragraph 0022-0025
[9]Current Patent Assignee: TEVA PHARMACEUTICAL INDUSTRIES LTD. - WO2004/106328, 2004, A1 Location in patent: Page 107
[10]Li, Shunlai; Zhou, Cheng; Yu, Mingwu; He, Qiwen; Du, Hongguang [Journal of Heterocyclic Chemistry, 2020, vol. 57, # 7, p. 2889 - 2903]

8
[ 1623-08-1 ]
[ 3056-17-5 ]
[ 244641-99-4 ]

Reference： [1]Tetrahedron,2001,vol. 57,p. 8129 - 8143

9
[ 49715-04-0 ]
[ 1623-08-1 ]
[ 258516-84-6 ]

Yield	Reaction Conditions	Operation in experiment
Ca. 48%	With tetrabutylammonium hydrogen sulfate; sodium hydrogencarbonate; In dichloromethane; water; at 0 - 20℃;	In one embodiment, another method of preparing the POM reagent dibenzyl(choloromethyl)phosphate, as shown in reaction Scheme 8 of FIG. 8. Briefly, dibenzylphosphate (10.6 g; 38.08 mmol) and chloromethyl sulfochloridate (7.52 g, 456.6 mmol/120 mL CH2Cl2) are dissolved in 320 mL water and 200 mL CH2Cl2 with NaHCO3 (12.80 g, 152.32 mmol) and n-Bu4NHSO4 (12.94 g, 38.08 mmol) at 0 C. to room temperature overnight, and then processed through a separation column with EA/H, EA. This reaction yields about 48% of dibenzyl(choloromethyl)phosphate (6 g), which is confirmed with TLC as shown

Reference： [1]Tetrahedron Letters,2002,vol. 43,p. 3793 - 3794
[2]Patent: JP2017/160205,2017,A .Location in patent: Page/Page column 135
[3]Patent: CN110279872,2019,A .Location in patent: Paragraph 0066
[4]Patent: US2015/111858,2015,A1 .Location in patent: Paragraph 0072

10
[ 33657-49-7 ]
[ 1623-08-1 ]
[ 1002109-24-1 ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate In acetone at 20℃;	8.A Example 8[[[(Bis(butylcarbonyloxymethoxy)phosphoryl)amino](imino)methyl](methyl)amino]acetic acid (11)Step A: [(Benzyloxy)(hydroxy)phosphoryl]oxy}methyl butyrate (12); Dibenzyl phosphate (2.8 g) was dissolved in 30 mL acetone and 1.8 g of chloromethyl butyrate and 8 g of cesium carbonate was added to the solution. The reaction mixture was stirred overnight at r.t. The solvent was removed, 100 mL of EtOAc added to the residue, and the suspension was filtered to remove the solid. After concentration of the filtrate, the acyloxy dibenzylphosphate was purified by silica gel chromatography using 25-50% EtOAc in hexane as the eluent. The purified acyloxy dibenzylphosphate was hydrogenated under 40 psi hydrogen in the presence of 300 mg of Pd/C. After removing the catalyst, the filtrate was concentrated to provide [(benzyloxy)(hydroxy)phosphoryl]oxy}methyl butyrate (12).

Reference： [1]Current Patent Assignee: AZURITY PHARMACEUTICALS INC - US2007/281909, 2007, A1 Location in patent: Page/Page column 52

11
[ 49715-04-0 ]
[ 1623-08-1 ]
[ 229625-50-7 ]

Yield	Reaction Conditions	Operation in experiment
59%	With tetra(n-butyl)ammonium hydrogensulfate; sodium hydrogencarbonate In dichloromethane; water	12.1 Phosphate Pro-drug (compound 138); Step 1: synthesis of P(OBut)2(=O)(OCH2CI) I I is synthesized according to the following scheme

Reference： [1]Current Patent Assignee: FORUM PHARMACEUTICALS INC; CHRONOGEN - WO2008/14602, 2008, A1 Location in patent: Page/Page column 59

12
[ 1623-08-1 ]
[ 21209-51-8 ]
[ 96675-10-4 ]

Reference： [1]Tetrahedron Asymmetry,2007,vol. 18,p. 2121 - 2124

13
1,4-anhydro-2,3,5-tri-O-benzyl-1-[3-hydroxypropyl-(R)-episulfoniumylidene]-D-arabinitol triflate [ No CAS ]
[ 1623-08-1 ]
1,4-anhydro-2,3,5-tri-O-benzyl-1-[3-dibenzylphosphorylpropyl-(R)-episulfoniumylidene]-D-arabinitol triflate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 20℃; for 3h;
81%	Stage #1: phosphoric acid dibenzyl ester With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 0℃; for 0.0666667h; Stage #2: 1,4-anhydro-2,3,5-tri-O-benzyl-1-[3-hydroxypropyl-(R)-episulfoniumylidene]-D-arabinitol triflate In tetrahydrofuran at 0 - 20℃; for 3h;	10; 5.2 Triphenylphosphine (2.4 mmol, 1.5 g), and diisopropyl azodicarboxylate (DIAD) (5.2 mmol, 0.46 mL) were stirred in anhydrous THF (5 mL) at 0° C. for 4 min. Dibenzyl phosphate (5.2 mmol, 1.46 g) was then added. After stirring the reaction mixture for an additional 4 min at 0° C., a solution of hydroxypropyl-2,3,5-tri-O-benzyl-1,4-dideoxy-1,4-thio-D-arabinitol (42) in THF (5 mL) was added dropwise at 0° C. under N2, and the reaction mixture was stirred for 3 h at room temperature. After the completion of the reaction, THF was removed in vacuo and the residue was purified by column chromatography to give compound (43) as a colorless oil (1.7 g, 81%). [α]D23 +3.0° (c=1.0, MeOH). 1H-NMR (CDCl3, 500 MHz): δ 7.36-7.169 (15H, m, 3Ph), 4.94-4.89 (4H, m, 2POCH2Ph), 4.60-4.47 (6H, m, 2CH2Ph, 1HACHPh, H-2), 4.31 (1H, d, JA,B=12.0 Hz, HbCHPh), 4.18(1H, d, J1a,1b=16.0 Hz, H-1a), 4.06 (1H, bs, H-3), 4.03-3.98(1H, m, H-3'a), 3.95(3H, m, H3'b, H-5a, H-4), 3.65-3.50(2H, m, H-5b, H-1'a), 3.48-3.3(2H, m, H-1'b, H-1b), 2.12-1.99(2H, m, H-2'). 13C-NMR (CDCl3, 125 MHz): δ 136.94, 136.24, 136.11(3Cipso), 129.0-128.1(3Ph), 128.3-119.6(CF3 triflate), 83.0(C-3), 82.5(C-2), 73.9(CH2Ph), 72.6(CH2Ph), 72.1(CH2Ph), 69.93(d, JC,P=5.75 Hz, POCH2Ph) 66.9(C-4), 66.5(C-5), 65.07(d, 2JC,P=5.75 Hz, C-3'), 47.5(C-1) 42.3(C-1'), 26.9(d, 3JC,P=6.12 Hz, C-2'). MALDI-TOF-MS: m/e 739.08 (M+-OTf). Anal. Calcd for C44H48F3O10PS2 C, 59.45; H, 5.44. Found: C, 59.11; H, 5.43.

Reference： [1]Bhat, Ramakrishna G.; Kumar, Nag S.; Pinto, B. Mario [Carbohydrate Research, 2007, vol. 342, # 12-13, p. 1934 - 1942]
[2]Current Patent Assignee: SIMON FRASER UNIVERSITY - US2007/244184, 2007, A1 Location in patent: Page/Page column 10-11; 21

14
[ 188905-38-6 ]
[ 1623-08-1 ]
N-(2-dibenzylphosphorylethyl)-2,3,5-tri-O-benzyl-1,4-dideoxy-1,4-imino-D-arabinitol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 20℃; for 3h;
76%	Stage #1: phosphoric acid dibenzyl ester With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 0℃; for 0.0833333h; Stage #2: 2-(2R,3R,4R)-3,4-bis(benzyloxy)-2-[(benzyloxy)methyl]-1-[(2-hydroxy)ethyl]-1H-pyrrolidine In tetrahydrofuran at 0 - 20℃; for 3h;	11; 5.2 To a well-stirred mixture of triphenylphosphine (3.35 mmol, 0.9 g), and diisopropyl azodicarboxylate (DIAD) (3.35 mmol, 0.65 mL) in anhydrous THF (5 mL) at 0° C., dibenzyl phosphate (3.35 mmol, 0.94 g) was added. After stirring the reaction mixture for 5 min at 0° C., a solution of N-hydroxyethyl-2,3,5-tri-O-benzyl-1,4-dideoxy-1,4-imino-D-arabinitol (39) (2.24 mmol, 1.0 g) in THF (5 mL) was added dropwise at 0° C. under N2, and the reaction mixture was stirred for 3 h at room temperature. After completion of the reaction, THF was removed in vacuo and the residue was purified by column chromatography (EtOAc:Hexanes, 4:6) to give compound (40) as a colorless oil (1.2 g, 76%). [α]D23 +26.0° (c=1.0, MeOH). 1H-NMR (CDCl3, 500 MHz): δ 7.25-7.17(25H, m, 5Ph), 5.07-4.92 (m, 4H, 2POCH2Ph), 4.42-4.29 (6H, m, 3OCH2Ph), 4.10-3.96(2H, m, H-2'), 3.82(1H, d, J2,3=5.0 Hz, H-2), 3.73 (1H, d, J3,4=3.7 Hz, H-3), 3.42 (2H, ddd, J5,4=6.0 Hz, J5a,5b=9.7 Hz, H-5), 3.16 (1H, d, J1a,1b=10.5 Hz, H-1a), 3.07 (1H, td, J1',2'=6.3 Hz, J1'a,1'b=12.9 Hz, H-1'a) 2.72 (1H, dd, J4,5=5.7 Hz, H-4), 2.57 (2H, m, H-1b, H-1'b). 13C-NMR (CDCl3, 125 MHz): δ 138.53, 138.36, 138.31, 136.22, 138.18 (5Cipso) 128.7-127.7(5*Ph), 85.3(C-3), 81.8(C-2), 73.4-71.5 (CH2Ph) 69.44 (d, JC,P=5.4 Hz, POCH2Ph), 68.1(d, 2JC,P=5.7 Hz, C-2'), 58.0(C-1), 54.84 (d, 3JC,P=6.6 Hz, C-1'). MALDI-TOF-MS: m/e 708.3 (M++H). Anal. Calcd for C42H46NO7P: C, 71.27; H, 6.55; N, 1.98. Found: C, 71.09; H, 6.50; N, 1.92.

15
[ 1623-08-1 ]
[ 4091-39-8 ]
[ 131444-73-0 ]

Yield	Reaction Conditions	Operation in experiment
49%	With caesium carbonate In DMF (N,N-dimethyl-formamide) at 20 - 80℃; for 6 - 9h;	5.2 To a stirred suspension of the appropriate phosphoric acid derivative 16 (10 mmol) and cesium carbonate (4.85 g, 15 mmol) in anhydrous DMF (15 mL) at room temperature under a nitrogen atmosphere was added dropwise a solution of the appropriate α-chloroketone 15 (11 mmol) in DMF (5 mL). After stirring at room temperature for 1 h the reaction mixture was stirred at 80°C for 5-8 h (monitored by tlc and/or LC/MS). The reaction mixture was filtered through a sintered funnel and the precipitate washed with ethyl acetate (2 x 10 mL). The combined filtrates were concentrated on rotavapor under reduced pressure. The residue was diluted with ethyl acetate (25 mL) and washed with brine (2 x 25 mL), dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel chromatography using a gradient of 0-50% ethyl acetate in hexane as eluent to give the pure 1-acylalkyl phosphate 17 in good yield. The 1-acylalkyl phosphates 17a-c were synthesized via Method 2.

Reference： [1]Current Patent Assignee: AZURITY PHARMACEUTICALS INC - WO2005/10011, 2005, A2 Location in patent: Page/Page column 42-43

16
3-(3',4',5'-trimethoxybezoyl)-7-methoxy-8-hydroxy-2H-chromene [ No CAS ]
[ 1623-08-1 ]
dibenzyl phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	Stage #1: 3-(3',4',5'-trimethoxybezoyl)-7-methoxy-8-hydroxy-2H-chromene; phosphoric acid dibenzyl ester With tetrachloromethane; N-ethyl-N,N-diisopropylamine In acetonitrile at -20℃; for 56h; Stage #2: With potassium dihydrogenphosphate In water; acetonitrile at -20 - 20℃;	6.iv To a stirred solution of the phenol (0.2 g, 0.54 mmol) in acetonitrile (1 ml) under Argon cooled to -20° C. was added carbon tetrachloride (0.26 ml, 2.70 mmol). The resulting solution was stirred for 10 minutes prior to adding diisopropylethylamine (0.21 ml, 1.13 mmol) and DMAP (0.0 μg, 0.11 mmol). Approximately 1 minute later, the slow dropwise addition of dibenzyl phosphate was done maintaining the temperature below -20° C. After 45 minutes, 0.5M KH2PO4 was added and the mixture was allowed to warm to room temperature. An ethyl acetate extract was washed with saturated sodium chloride (aq), followed by water and dried. Removal of the solvent in vacuo gave a yellow oil that was further separated by silica gel chromatography (flash, 60:40, hexane-ethyl acetate) to afford (0.34 g, 0.54 mmol, 100%) of the dibenzylphosphate as a clear green oil

Reference： [1]Current Patent Assignee: MATEON THERAPEUTICS INC - US2005/245489, 2005, A1 Location in patent: Page/Page column 10

17
[ 537-42-8 ]
[ 1623-08-1 ]
[ 1028098-06-7 ]

Yield	Reaction Conditions	Operation in experiment
		Example 22: (E) -4- (3, 5-dimethoxystyryl)phenyl dihydrogen phosphate ARSl 4.; To a cold mixture (-100C) of <strong>[537-42-8]pterostilbene</strong> (200mg, 0.67mM) and N,N- (dimethylamino) pyridine (10.2mg, 0.083mM) in anhydrous acetonitrile (1OmL) was added carbon tetrachloride (323muL, 3.35mM) and DIEA (245muL, 1.4mM) . The mixture was left stirring at -100C for 30 min and dibenzyl phosphate (224muL, ImM) was added. The solution was stirred for 12h at <n="30"/>room temperature and poured into 0.5M monobasic potassium phosphate. The mixture was extracted with ethyl acetate and the organic phase dried over MgSO4. The solvent was evaporated, the crude mixture was purified by column chromatography eluting with hexanes : ethyl acetate (7:3) and afforded (E)- dibenzyl 4- (3, 5-dimethoxystyryl) phenyl phosphate.

Reference： [1]Patent: WO2008/70872,2008,A1 .Location in patent: Page/Page column 27-28

18
[ 1623-08-1 ]
[ 265983-71-9 ]
C₂₃H₂₁O₇P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	Stage #1: 2,2,2-trifluoroethyl (2'-hydroxy-3',5'-dimethyl)phenoxyacetate With lead oxide; acetic acid In chloroform for 0.166667h; Stage #2: phosphoric acid dibenzyl ester In chloroform at 25 - 40℃; for 44h;	16 To a solution of 2,2,2-trifluoroethyl (2'-hydroxy-3',5'-dimethyl) phenoxyacetate (21.2 mg, 0.076 mmol) in chloroform (25.0 mL) was added lead (IV) oxide (2.5 g) and acetic acid (3.3 mL). The suspension was stirred for 10 min and the solid was filtered. The resulting yellow solution was added to dibenzylphosphoric acid (42.4 mg, 2 equiv). The reaction solution was stirred at 25° C. for 20 h and then at 40° C. for 24 h. The reaction solution was passed through a DEAE-cellulose resin (dry, pretreated with chloroform) to afford the crude trapped trialkylphosphate 16 (23.0 mg) in 66% yield as an off-color solid. [00795] 1 H NMR (CD3CN) ¶7.36-7.33 (m, 10H, 2C6H5), 6.86 (s, 2H, C6H2), 5.01 (d, J=8.16 Hz, 4H, 2CH2C6H5), 4.90 (d, J=8.66 Hz, 2H, CH2C6H2), 4.66 (s, 2H, OCH2CO), 2.23 (s, 3H, CH3); 31P NMR d 8.75

Reference： [1]Current Patent Assignee: UNIVERSITY OF ARKANSAS SYSTEM - US6657052, 2003, B1 Location in patent: Page column 93

19
[ 6974-29-4 ]
[ 1623-08-1 ]
[ 1094764-69-8 ]

Yield	Reaction Conditions	Operation in experiment
35%	Stage #1: phosphoric acid dibenzyl ester With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere; Stage #2: N-(2-hydroxyethyl)-2,2,2-trifluoroacetamide With pyridine; 4 A molecular sieve In dichloromethane at 0 - 20℃; for 4h; Inert atmosphere;	Dibenzyl phosphate (1.5 eq) was dissolved in DMF and CH2CI2, and the resulting solution was cooled to 0 0C. Oxalyl chloride (3.0 eq) was added dropwise under an argon atmosphere. The solution was allowed to warm to room-temperature, and was stirred for 1 h. The solvent was removed in vacuo and the remaining material was azeotroped with toluene. The resulting viscous liquid was dissolved in CH2CI2 and added dropwise to a flask containing 1 and 4 A molecular sieves (ca. 5-10) in pyridine at 0 0C. The solution was stirred under an argon atmosphere for 1 h at 0 0C and then for 3h at room-temperature. The solvent was removed in vacuo and the product was purified by silica gel chromatography (1 :1 →1 :2 Hexane/EtOAc) to afford 2. Following general procedure II, dibenzyl phosphate (1.79 g, 6.45 mmol) was dissolved in DMF (10 μl_) and CH2CI2 (25 ml_) and combined with oxalyl chloride (1.13 ml_, 12.9 mmol). After concentration, the compound was redissolved in CH2CI2 (5 ml_) and added to 1 a (675 mg, 4.3 mmol) in pyridine (10 ml_) and 4 A molecular sieves to yield 621 mg (35%) of 2a as an off-white solid. 1H (300 MHz, CDCI3): δ 7.35 (m, 10H), 5.03 (ABX system, 4H, JAB = 15 Hz, JAP = JBP = 11.7 Hz), 4.04 (pentet, 2H, J = 4.8 Hz), 3.50 (q, 2H, J = 5.1 ). 13C (75 MHz, CDCI3): δ 135.45, 129.00, 128.12, 70.02, 65.7, 40.49. ESI-MS calcd for C18H19F3NO5P [M + H] +: 418.1031 found 418.1019.

Reference： [1]Current Patent Assignee: WARF (in: University of Wisconsin); UNIVERSITY OF WISCONSIN SYSTEM - WO2009/132310, 2009, A1 Location in patent: Page/Page column 67

20
[ 1623-08-1 ]
8-methoxy-1-methyl-1H-benzo[de][1,6]naphthyridin-9-ol hydrochloride [ No CAS ]
[ 680615-39-8 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 8-methoxy-1-methyl-1H-benzo[de][1,6]naphthyridin-9-ol hydrochloride With N-ethyl-N,N-diisopropylamine In tetrachloromethane; acetonitrile at -10℃; for 0.0333333h; Stage #2: phosphoric acid dibenzyl ester In tetrachloromethane; acetonitrile at -10℃; for 2h;	Synthesis of Hystatin 1 (Disodium isoaaptamine 9-O-phosphate) (11). To a dry flask equipped with a septum, magnetic stirrer, thermometer and Ar inlet containing dry acetonitrile (20 mL) was added isoaaptamine hydrochloride (2, 0.26 g, 0.97 mmol). Upon cooling to -10 C., tetrachloromethane (0.47 mL, 4.85 mmol) was added followed by diisopropylethylamine (0.51 mL, 2.91 mmol) and a catalytic amount of dimethylaminopyridine. After 2 minutes, dropwise addition of dibenzyl phosphate (0.30 mL, 1.36 mmol) was begun while maintaining a temperature of -10 C. The resultant yellow solution was stirred for 2 hours and 0.5 M aqueous KH2PO4 (30 mL) was added. The water layer was extracted with CH2Cl2 (450 mL) and the combined organic extract was washed with brine (100 mL). The organic layer was dried and the solvent was removed in vacuo. Purification by column chromatography (neutral alumina, CH2Cl2-CH3OH, 20:1 as eluent) gave the dibenzyl phosphate as a yellow oil (0.27 g) which was immediately dissolved in dichloromethane. Bromotrimethylsilane (0.2 mL) was added at room temperature. After stirring for 2 hours, the solvent was removed and the residue was dissolved in water (20 mL). The water layer was washed with dichloromethane (310 mL) and the water was removed. The yellow solid was dissolved in methanol, a 30% solution of sodium methoxide (0.22 mL, 1.16 mmol) was added and the mixture was stirred for 12 hours. The reaction mixture was concentrated to a yellow solid that was recrystallized from acetone-water. The isoaaptamine prodrug (11) was obtained as a yellow-green powder (0.15 g, 45% yield): mp 166-168 C. (dec.); UV (CH3OH) 8max (log ?) 209 nm (4.22), 241 (4.17), 260 (4.28), 316 (3.49), 326 (3.39), 389 (3.78); IR (KBr): v 3406 (s), 3227 (m), 1649 (s), 1604 (s), 1525 (w), 1465 (m), 1429 (w), 1342 (m), 1298 (m), 1240 (w), 1111 (s), 977 (s), 848 (m), 723 (m), 630 (m), 563 (m); 1H NMR (D2O and a few drops of CD3OD): 3.77 (s, 3H, NMe), 3.87 (s, 3H, OMe), 5.84 (d, J=7.5 Hz, 1H, H-3), 6.47 (d, J=7.5 Hz, 1H, H-6), 6.62 (d, J=7.5 Hz, 1H, H-5), 6.65 (s, 1H, H-7), 7.43 (d, J=7.5 Hz, 1H, H-2); 13C NMR (D2O): =45.81, 56.32, 98.05, 101.49, 112.90, 117.34, 128.96, 132.80, 134.10, 147.76, 148.32, 158.62; 31P NMR (162 MHz, D2O) *1.58; EIMS m/z 228 (100) [M+-(NaO)2P(O)H], 213 (58), 185 (39), 170 (24), 142 (13), 114 (12), 28 (31); HRFABMS ([M-Na2O3P+H] m/z 229.09392 (cald for C13H13N2O2, 229.09771).

Reference： [1]Current Patent Assignee: ARIZONA BOARD OF REGENTS - US2005/187240, 2005, A1 Location in patent: Page/Page column 5; 7

21
[ 591-80-0 ]
[ 1623-08-1 ]
[ 1228321-59-2 ]

Yield	Reaction Conditions	Operation in experiment
85%	With [bis(acetoxy)iodo]benzene In acetonitrile at 20℃; for 2h;
71%	With ammonium iodide; 3-chloro-benzenecarboperoxoic acid In [⁽²⁾H₆]acetone at 20℃; for 8h;	NH4I catalytic phosphoryloxylactonisation of alkenoic acids; typicalprocedure General procedure: To CH3CN (5 mL), pent-4-enoic acid (0.030 g, 0.3 mmol), diphenylphosphate (0.090 g, 0.36 mmol), mCPBA (75%, 0.138 g, 0.60 mmol)and NH4I (0.0043 g, 0.030 mmol) were added. The mixture wasstirred at room temperature for 8 h. Then H2O (5 mL), sat.aq Na2S2O3(2 mL) and sat. aq Na2CO3 (2 mL) were added. The mixture wasextracted with CH2Cl2 (3 × 5 mL) and the combined organic extractwas dried over anhydrous Na2SO4, filtered, and concentrated underreduced pressure. The residue was purified on silica gel plate using(3 : 2 hexane-ethyl acetate) as eluent to afford 5-(bis(phenyloxy)phosphoryl)oxy-4-pentanolactone in 71% yield.
70%	With iodobenzene; 3-chloro-benzenecarboperoxoic acid; trifluoroacetic acid at 20℃; for 8h;

Reference： [1]Location in patent: experimental part Zhou, Zhong Shi; He, Xue Han [Chinese Chemical Letters, 2010, vol. 21, # 9, p. 1041 - 1044]
[2]Zhou, Zhong-Shi; He, Xue-Han [Journal of Chemical Research, 2014, vol. 38, # 10, p. 630 - 633]
[3]Location in patent: experimental part Zhou, Zhong-Shi; He, Xue-Han [Tetrahedron Letters, 2010, vol. 51, # 18, p. 2480 - 2482]

22
[ 1575-74-2 ]
[ 1623-08-1 ]
[ 1228321-60-5 ]

Yield	Reaction Conditions	Operation in experiment
71%	With iodobenzene; 3-chloro-benzenecarboperoxoic acid; trifluoroacetic acid at 20℃; for 8h;
68%	With ammonium iodide; 3-chloro-benzenecarboperoxoic acid In acetonitrile at 20℃; for 8h;	NH4I catalytic phosphoryloxylactonisation of alkenoic acids; typicalprocedure General procedure: To CH3CN (5 mL), pent-4-enoic acid (0.030 g, 0.3 mmol), diphenylphosphate (0.090 g, 0.36 mmol), mCPBA (75%, 0.138 g, 0.60 mmol)and NH4I (0.0043 g, 0.030 mmol) were added. The mixture wasstirred at room temperature for 8 h. Then H2O (5 mL), sat.aq Na2S2O3(2 mL) and sat. aq Na2CO3 (2 mL) were added. The mixture wasextracted with CH2Cl2 (3 × 5 mL) and the combined organic extractwas dried over anhydrous Na2SO4, filtered, and concentrated underreduced pressure. The residue was purified on silica gel plate using(3 : 2 hexane-ethyl acetate) as eluent to afford 5-(bis(phenyloxy)phosphoryl)oxy-4-pentanolactone in 71% yield.

Reference： [1]Location in patent: experimental part Zhou, Zhong-Shi; He, Xue-Han [Tetrahedron Letters, 2010, vol. 51, # 18, p. 2480 - 2482]
[2]Zhou, Zhong-Shi; He, Xue-Han [Journal of Chemical Research, 2014, vol. 38, # 10, p. 630 - 633]

23
[ 16386-93-9 ]
[ 1623-08-1 ]
[ 1228321-61-6 ]

Yield	Reaction Conditions	Operation in experiment
76%	With ammonium iodide; 3-chloro-benzenecarboperoxoic acid; In acetonitrile; at 20℃; for 8h;	General procedure: To CH3CN (5 mL), pent-4-enoic acid (0.030 g, 0.3 mmol), diphenylphosphate (0.090 g, 0.36 mmol), mCPBA (75%, 0.138 g, 0.60 mmol)and NH4I (0.0043 g, 0.030 mmol) were added. The mixture wasstirred at room temperature for 8 h. Then H2O (5 mL), sat.aq Na2S2O3(2 mL) and sat. aq Na2CO3 (2 mL) were added. The mixture wasextracted with CH2Cl2 (3 × 5 mL) and the combined organic extractwas dried over anhydrous Na2SO4, filtered, and concentrated underreduced pressure. The residue was purified on silica gel plate using(3 : 2 hexane-ethyl acetate) as eluent to afford 5-(bis(phenyloxy)phosphoryl)oxy-4-pentanolactone in 71% yield.

Reference： [1]Chinese Chemical Letters,2010,vol. 21,p. 1041 - 1044
[2]Journal of Chemical Research,2014,vol. 38,p. 630 - 633
[3]Tetrahedron Letters,2010,vol. 51,p. 2480 - 2482

24
[ 847440-49-7 ]
[ 1623-08-1 ]
[ 1254702-92-5 ]

Yield	Reaction Conditions	Operation in experiment
80%	With N-iodo-succinimide In tetrahydrofuran; dichloromethane at 20℃; for 5h; Molecular sieve; Inert atmosphere;	1.2 Step 2: A solution of 14-O-methylthiomethyltriptolide (50 mg, 0.12 mmol) in dry methylene chloride (2 mL) under an N2 atmosphere was combined with powdered activated 4A molecular sieves (50 mg), followed by the addition of a mixture of dibenzylphosphate (40 mg, 0.14 mmol) and N-iodosuccinimide (32 mg, 0.14 mmol) in tetrahydrofuran (2 mL). The reaction mixture was stirred at room temperature for a period of 5 hours, filtered, and diluted with methylene chloride (20 mL). The resulting solution was washed with a solution of sodium thiosulfate (2 mL, IM solution), a saturated solution of sodium bicarbonate, brine, dried over a sodium sulfate, filtered, and concentrated in vacuo. The oily residue was purified by silica gel flash chromatography (1 :2 hexane/ethyl acetate) to give 14-O-phosphonooxymethyltriptolide dibenzyl ester (62 mg, 80% yield) as a white foam. 1H NMR (400 MHz, CDCl3) δ 0.72 (d, 3H, J = 6.8 Hz), 0.89 (d, 3H, J = 6.8 Hz), 1.05 (s, 3H), 1.27 (m, IH), 1.48 (m, IH), 1.82 (dd, IH5 J7 = 14.7 and J2= 13.4 Hz), 2.03-2.35 (m, 4H)5 2.64 (m, IH), 3.14 (d, IH5 J = 5.5 Hz), 3.46 (d, IH5 J = 3.1 Hz), 3.65 (s, IH)5 3.76 (d, IH5 J = 3.1 Hz)5 4.65 (m, 2H)5 5.02 (m, 4H), 5.27 (m, IH)5 5.47 (m, IH)5 7.34 (m, 10H) ppm; 13C NMR (100 MHz5 CDCl3) δ 13.6, 16.8, 17.0, 23.3, 26.2, 29.62, 29.67, 35.7, 40.3, 54.7, 55.2, 59.3, 61.1, 63.6, 64.0, 69.36, 69.39, 69.42, 69.45, 69.9, 78.2, 92.9,09531.293WO1 - Z09023 93.0, 125.5, 127.9, 128.0, 128.6, 135.5, 135.6, 160.1, 173.2 ppm; HRMS calculated for (C35H39O10PNa) required m/z [M+Na]+ 673.2179, found m/z 673.2176.
80%	With N-iodo-succinimide In tetrahydrofuran; dichloromethane at 20℃; for 5h; Inert atmosphere; Molecular sieve;	3.b b. A solution of 14-O-methylthiomethyltriptolide (50 mg, 0.12 mmol) in dry methylene chloride (2 mL) under an N2 atmosphere was combined with powdered activated 4 Å molecular sieves (50 mg), followed by the addition of a mixture of dibenzylphosphate (40 mg, 0.14 mmol) and N-iodosuccinimide (32 mg, 0.14 mmol) in tetrahydrofuran (2 mL). The reaction mixture was stirred at room temperature for a period of 5 hours, filtered, and diluted with methylene chloride (20 mL). The resulting solution was washed with a solution of sodium thiosulfate (2 mL, 1M solution), a saturated solution of sodium bicarbonate, brine, dried over a sodium sulfate, filtered, and concentrated in vacuo. The oily residue was purified by silica gel flash chromatography (1:2 hexane/ethyl acetate) to give 14-O-phosphonooxymethyltriptolide dibenzyl ester (62 mg, 80% yield) as a white foam. 1H NMR (400 MHz, CDCl3) δ 0.72 (d, 3H, J=6.8 Hz), 0.89 (d, 3H, J=6.8 Hz), 1.05 (s, 3H), 1.27 (m, 1H), 1.48 (m, 1H), 1.82 (dd, 1H, J1=14.7 and J2=13.4 Hz), 2.03-2.35 (m, 4H), 2.64 (m, 1H), 3.14 (d, 1H, J=5.5 Hz), 3.46 (d, 1H, J 3.1 Hz), 3.65 (s, 1H), 3.76 (d, 1H, J=3.1 Hz), 4.65 (m, 2H), 5.02 (m, 4H), 5.27 (m, 1H), 5.47 (m, 1H), 7.34 (m, 10H) ppm; 13C NMR (100 MHz, CDCl3) δ 13.6, 16.8, 17.0, 23.3, 26.2, 29.62, 29.67, 35.7, 40.3, 54.7, 55.2, 59.3, 61.1, 63.6, 64.0, 69.36, 69.39, 69.42, 69.45, 69.9, 78.2, 92.9, 93.0, 125.5, 127.9, 128.0, 128.6, 135.5, 135.6, 160.1, 173.2 ppm; HRMS calculated for (C35H39O10PNa) required m/z [M+Na]+ 673.2179, found m/z 673.2176.

Reference： [1]Current Patent Assignee: UNIVERSITY OF MINNESOTA SYSTEM - WO2010/129918, 2010, A1 Location in patent: Page/Page column 23-24
[2]Current Patent Assignee: MINNEAMRITA THERAPEUTICS - US2020/85784, 2020, A1 Location in patent: Paragraph 0096; 0098

25
[ 1623-08-1 ]
[ 1256913-34-4 ]
[ 1256913-35-5 ]

Yield	Reaction Conditions	Operation in experiment
60%	With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 20℃; for 6h;	Ethyl 1 -[(2S)-I- [bis(benzyloxy)phosphorylloxy}-4-methylpentan-2-yll-6-bromo-4-oxo- 1.4- dihydro- 1.8-naphthyridine-3 -carboxylateEthyl (2Z)-2-[(5-bromo-2-chloropyridin-3-yl)carbonyl]-3-[(2S)-l-hydroxy-4-methylpentan-2-yl]amino} prop-2-enoate (Intermediate 27, 415 mg, 0.95 mmol) and triphenylphosphine (409 mg, 1.47 mmol) were dissolved in tetrahydrofuran (30 mL). Diisopropyl azodicarboxylate [DIAD] (0.4 mL, 2.35 mmol) was added and the mixture was stirred for 1 h at room temperature. A second portion of triphenylphosphine (625 mg) and diisopropyl azodicarboxylate [DIAD] (0.4 mL) were added and the mixture was stirred for an additional 5 h at room temperature. The reaction mixture was concentrated under reduced pressure to give a crude compound. The crude compound was purified by flash column chromatography over silica gel (10 - 30 % ethyl acetate / petrolleum ether to afford 700 mg (60%) of ethyl 1-[(2S)- l-[bis(benzyloxy)phosphoryl]oxy}-4-methylpentan-2-yl]-6-bromo-4-oxo-l,4-dihydro-l,8- naphthyridine-3-carboxylate as liquid.1H NMR (400 MHz. DMSO-dfi): δ 0.94 (d, 6H), 1.24 (t, 3H), 1.38 (d, IH), 1.66 (d, IH), 1.88 (d, IH), 4.22 (q, 2H), 4.48 (2s, 2H), 4.85 (d, 4H), 6.01 (d, IH), 7.15-7.41 (m, 10H), 8.62 (s, IH), 8.79 (s, IH), 8.97 (s, IH). LC-MS: m/z 659 (M+H).

Reference： [1]Current Patent Assignee: ASTRAZENECA PLC - WO2010/136817, 2010, A1 Location in patent: Page/Page column 122-123

26
[ 1623-08-1 ]
[ 1256913-30-0 ]
[ 1256913-32-2 ]

Yield	Reaction Conditions	Operation in experiment
40%	With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 20℃; for 4h;	2-{rBis(benzyloxy)phosphoryl1oxy}ethyl 6-bromo- 1 -ethyl-4-oxo- 1,4-dihydro- 1,8- naphthyridine-3 -carboxylate2-Hydroxyethyl 6-bromo- 1 -ethyl-4-oxo- 1 ,4-dihydro- 1 ,8 -naphthyridine-3 -carboxylate (Intermediate 23, 100 mg, 0.29 mol), dibenzyl hydrogen phosphate (65 mg, 0.23 mmol) and triphenylphosphine (192 mg, 0.733 mmol) were dissolved in tetrahydrofuran (15 mL). Diisopropyl azodicarboxylate [DIAD] (106 mg, 0.52 mmol) was added drop wise and the mixture was stirred for 4 h at room temperature. The reaction mixture was concentrated under reduced pressure and water (100 mL) was added. The aqueous mixture was extracted with ethyl acetate (2 x 100 mL) and the combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to give a crude compound. The crude compound was purified by flash column chromatography over silica gel (10- 50% ethyl acetate / petroleum ether) to afford 60 mg (40%) of 2- { [bis(benzyloxy)phosphoryl]oxy } ethyl 6-bromo- 1 -ethyl-4-oxo- 1 ,4-dihydro- 1,8- naphthyridine-3 -carboxylate. 1H NMR (400 MHz. DMSO-dfi): δ 1.36 (t, 3H), 4.04 (m, IH), 4.2-4.44 (m, 5H), 5.02 (m, 4H), 7.28 (m, 10H), 8.59 (s, IH), 8.94 (s, IH), 8.99 (s, IH) LC-MS: m/z 601 (M+H).

Reference： [1]Current Patent Assignee: ASTRAZENECA PLC - WO2010/136817, 2010, A1 Location in patent: Page/Page column 120-121

27
[ 1623-08-1 ]
[ 1256913-31-1 ]
[ 1256913-33-3 ]

Yield	Reaction Conditions	Operation in experiment
47%	With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 20℃; for 4h;	3-[Bis('benzyloxy)phosphoryl1oxy}propyl 6-bromo-l-ethyl-4-oxo-l,4-dihydro-l,8- naphthyridine-3 -carboxylate3 -Hydroxypropyl 6-bromo- 1 -ethyl-4-oxo- 1 ,4-dihydro- 1 , 8-naphthyridine-3 -carboxylate (Intermediate 24, 100 mg, 0.28 mmol), dibenzyl hydrogen phosphate (124 mg, 0.44 mmol) and triphenylphosphine (367 mg, 1.4 mmol) was dissolved in tetrahydrofuran (15 mL). Diisopropyl azodicarboxylate [DIAD] (281 mg, 1.40 mmol) was added and the mixture was stirred for 4 h at room temperature. The reaction mixture was concentrated under reduced pressure and water (100 mL) was added. The aqueous mixture was extracted with ethyl acetate (2 x 100 mL) and the combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to give a crude compound. The crude compound was purified by flash column chromatography over silica gel (0 - 50% ethyl acetate / petrolleum ether) to afford 80 mg (47%) of 3-{ [bis(benzyloxy)phosphoryl] oxy } propyl 6-bromo- 1 -ethyl-4-oxo- 1 ,4-dihydro- 1,8- naphthyridine-3 -carboxylate NMR (CHCh): δ 1.44 (t, 3H), 2.08 (q, 2H), 4.21 (q, 2H), 4.41 (m, 4H), 5.02 (m, 2H), 7.27 (m, 10H), 8.81 (s, IH), 8.86 (s, IH), 8.92 (s, IH).

Reference： [1]Current Patent Assignee: ASTRAZENECA PLC - WO2010/136817, 2010, A1 Location in patent: Page/Page column 120

28
[ 1623-08-1 ]
[ 1221157-00-1 ]
[ 1334725-14-2 ]

Yield	Reaction Conditions	Operation in experiment
88%	With tetrachloromethane; dmap; N-ethyl-N,N-diisopropylamine In acetonitrile at -10 - -2.5℃; for 3.5h; Inert atmosphere;	7.1 Embodiment 7; Preparation (phosphate esterification 2) of 3,4,5-trimethoxy-4'-ethoxydiphenylethane-3'-0-disodium phosphate salt (hereinafter referred to as the code: ECB1 P); Step 1: under the atmosphere of argon, 4.2 grams of 3,4,5-trimethoxy-3-hydroxy-4-ethoxydiphenylethane (12.6mmol.) is added into a four-necked flask and is then dissolved with 40mL of dry acetonitrile and cooled to -2.5°C, 6ml of carbon tetrachloride is then added, 4.7ml of diisopropylethylamine and 0.15 grams of 4-dimethylaminopyridine are added after stirring is continuously stirred for 5 minutes, 1 minute later, 4ml of dibenzyl phosphate (80%) is slowly added, the temperature is kept below -10°C, reaction is continuously performed for 3.5 hours while TLC tracking is implemented, 10m of 10.5M KH2P04 is added upon complete reaction, followed by natural rise of the temperature to room temperature, extraction with ethyl acetate, merging of organic layers, sequential washing with distilled water and saturated saline water, drying with anhydrous magnesium sulfate and reduced pressure distillation of solvent to obtain muddy oily matters, the oily matters are subjected to recrystallization by ethyl acetate-n-hexane to obtain 6.6 grams of colorless needle crystals, and the yield is 88%.

Reference： [1]Current Patent Assignee: ZHEJIANG WILDWIND PHARMACEUTICAL; SHANGHAI ECUST BIOMEDICINE - EP2351730, 2011, A1 Location in patent: Page/Page column 11

29
[ 3518-65-8 ]
[ 1623-08-1 ]
[ 258516-84-6 ]

Yield	Reaction Conditions	Operation in experiment
74.1%	With sodium hydrogencarbonate; tetrabutylammonium sulfate; In dichloromethane; water; at 20℃;Cooling with ice;	Step 1: Dibenzyl Chloromethyl Phosphate (33B) Dibenzyl phosphate (33A) (5.0 g, 0.018 mol) was dissolved into a mixture of dichloromethane (50 mL) and water (50 mL), then, tetrabutylammonium sulphate (1.22 g, 0.0036 mol) and sodium bicarbonate (6.0 g, 0.072 mol) was added under ice-water bath, followed by adding chloromethanesulfonyl chloride (2.97 g, 1.9 mL), and the mixture was stirred overnight at room temperature, stood and separated, and extracted with dichloromethane (50 mL). The combined organic extracts were washed with saturated brine (100 mL*2), dried over anhydrous sodium sulfate, concentrated under reduced pressure. The residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate (v/v)=5:1?3:1, gradient elution) to afford dibenzyl chloromethyl phosphate (33B) as a colorless liquid (4.35 g, yield: 74.1%). 1H NMR (400 MHz, CDCl3): delta 7.36-7.26 (m, 10H), 5.63 (d, 2H), 5.10 (d, 4H).
74.1%	With tetra(n-butyl)ammonium hydrogensulfate; sodium hydrogencarbonate; In dichloromethane; water; at 20 - 30℃;Cooling with ice;	Dibenzyl phosphate (33A) (5.0 g, 0.018 mol) was dissolved into a mixture of dichloromethane (50 mL) and water (50 mL), then,tetrabutylammonium sulphate (1.22 g, 0.0036 mol) and sodium bicarbonate (6.0 g, 0.072 mol) was added under icewaterbath, followed byadding chloromethanesulfonyl chloride (2.97 g, 1.9 mL), and the mixture was stirred overnight at room temperature, stood and separated, andextracted with dichloromethane (50 mL). The combined organic extracts were washed with saturated brine (100 mL×2), dried over anhydroussodium sulfate, concentrated under reduced pressure. The residue was purified by silica gel column chromatography (petroleum ether/ethylacetate (v/v)=5:1?3:1, gradient elution) to afford dibenzyl chloromethyl phosphate (33B) as a colorless liquid (4.35 g, yield: 74.1%).

Reference： [1]Patent: US2016/60197,2016,A1 .Location in patent: Paragraph 0362; 0363; 0364; 0365
[2]Patent: KR2016/5361,2016,A .Location in patent: Paragraph 1019; 1022; 1023-1025
[3]Journal of the American Chemical Society,2011,vol. 133,p. 12021 - 12030

30
[ 1623-08-1 ]
[ 1345664-83-6 ]
[ 1345664-84-7 ]

Yield	Reaction Conditions	Operation in experiment
97%	With triethylamine; triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran; toluene at 20℃; for 15h; Inert atmosphere;
97%	With triethylamine; triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran; toluene at 20℃; for 15h; Inert atmosphere;	1.5 Step 5: Methyl 7-0-dibenzylphosphate-2 , 3 , 4 , 6-tetra- benzyl-D-glycero-a-D-gluco-heptopyranosideTo the previous alcohol (250 mg, 0.43 mmol, 1 eq.), PPh3 (485 mg, 1.85 mmol, 4.3 eq.), dibenzylphosphate (515 mg, 1.85 mmol, 4.3 eq.), and Et3 (500 yL, 3.60 mmol) in solution in distilled THF (3.5 mL) , was slowly added diethyl azodicarboxylate 40% in solution in toluene (820 yL, 1.85 mmol, 4.3 eq.) under argon atmosphere at room temperature. The reaction mixture was light yellow. After 15 hours, the solvent was removed in vacuo. Purification of the residue by flash chromatography (Si02, Cyclohexane/EtOAc 8:2 to 7:3) afforded the desired product (360 mg, 97%) .[ ]d20 (CHC13, c=l) = +19.8 0.31P NMR (101 MHz, CDCI3) δ (ppm) -0.29.XH NMR (400 MHz, CDCI3 ) δ (ppm) 7.38-7.17 (m, 30H, Harom) , 5.01-4.91 (m, 5H, CH2Bn) , 4.84 (d, J= 11.0Hz, 1H, CH2Bn) , 4.77 (d, J= 10.8Hz, 1H, CH2Bn) , 4.76 (d, J= 10.5Hz, 1H, CH2Bn) , 4.64 (d, J= 10.9Hz, 2H, CH2Bn) , 4.55 (d, J= 11.7Hz, 2H, CH2Bn) , 4.54 (d, J= 3.7Hz, 1H, H-l), 4.15 (m, 2H, H-7), 3.96 (t, J= 9.2Hz, 1H, H-3), 3.91 (m, 1H, H-6), 3.85 (d, J= 10.5Hz, 1H, H-5), 3.50 (dd, J= 10.3Hz, J= 8.9Hz, 1H, H-4), 3.43 (dd, J= 9.9Hz, J= 3.7Hz, 1H, H-2) , 3.34 (s, 3H, HMe) .13C NMR (100 MHz, CDC13) δ (ppm) 138.7-135.8 (6Cqarom), 128.6-127.7 (30CHarom), 97.9 (C-l), 82.4 (C-3), 80.0 (C- 2), 78.1 (d, J= 7.7Hz, C-6) , 77.9 (C-4), 75.9 74.9 73.4 72.9 (4CH2Bn), 70.5 (C-5), 69.3 (app.t, J= 4.8Hz, 2CH2Bn) , 67.6 (d, J = 5.8Hz, C-7), 55.3 (CMe) .MS (ESI+ ) : m/z: 867.33(100%) [M+Na]+, 607.27(60%)[C36H4o07+Na] +, 862.37 (60%) [M+NH4]+, 279.09 (20%) [Ci4H1504P+H] + .HRMS (TOF-MS-ESI+ ) : calculated for C5oH530i0P a, [M+Na]+ : 867.3269, found: 867.3265.Elemental analysis: calculated (%) for C50H53O10P : C 71.08, H 6.32; found: C 70.62, H 6.64.

Reference： [1]Durka, Maxime; Tikad, Abdellatif; Périon, Régis; Bosco, Michael; Andaloussi, Mounir; Floquet, Stéphanie; Malacain, Elodie; Moreau, François; Oxoby, Mayalen; Gerusz, Vincent; Vincent, Stéphane P. [Chemistry - A European Journal, 2011, vol. 17, # 40, p. 11305 - 11313]
[2]Current Patent Assignee: PHARMA OMNIUM INTERNATIONAL P O I - WO2012/73214, 2012, A2 Location in patent: Page/Page column 24

31
[ 1623-08-1 ]
[ 98-86-2 ]
[ 1360473-97-7 ]

Yield	Reaction Conditions	Operation in experiment
58%	With iodobenzene; 3-chloro-benzenecarboperoxoic acid In acetonitrile at 20℃; for 24h; regioselective reaction;
25%	With tert.-butylhydroperoxide; tetra-(n-butyl)ammonium iodide In water at 75℃; for 24h;	General procedure of ketol phosphates General procedure: A 70 wt% tert-butyl hydroperoxide solution in H2O (TBHP, 3.0mmol), was added dropwise for 15min into the mixture of acetophenone derivatives (2.0mmol), TBAI (20mol%), and dialkyl or diaryl phosphite or H-phosphine oxide (1.0mmol) in water (H2O, 2.0mL). The resulting mixture was stirred at 75°C for 24h. The progress of the reaction was monitored by thin layer chromatography (TLC). After the completion of the reaction, the resulting solution was cooled to room temperature. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate and dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel using petroleum ether/ethyl acetate as an eluent and the products were characterized by 1H, 13C, 31P NMR, IR, ESI, and HRMS analysis.

Reference： [1]Location in patent: experimental part Pu, Ye; Gao, Liumian; Liu, Huijun; Yan, Jie [Synthesis, 2012, vol. 44, # 1, p. 99 - 103]
[2]Saidulu; Arun Kumar; Anitha; Santhosh Kumar; Reddy, K. Rajender [Tetrahedron Letters, 2016, vol. 57, # 15, p. 1648 - 1652]

32
[ 1623-08-1 ]
[ 1345664-76-7 ]
thiophenyl 1-deoxy-2,3,4,6-tetra-O-benzyl-7-(dibenzyloxyphosphoryl)-D-glycero-α-D-mannoheptopyranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With triethylamine; diethylazodicarboxylate In tetrahydrofuran; toluene at 20℃; for 24h;	2.6 Step 6: Thiophenyl l-deoxy-2 , 3 , 4 , 6-tetra-0-benzyl-7- (dibenzyloxyphosphoryl) -D-glycero-3 (0.393 g, 1.5 mmol), dibenzylphosphate (0.417 g, 1.5 mmol) and triethylamine (417 mL, 3 mmol) in THF (2 mL) was prepared. Diethylazidocarboxylate 90 % in toluene (235 yL, 1.5 mmol) was slowly added and the mixture was stirred for 24 h at room temperature. After concentration, the residue was purified by flash silica gel chromatography (cyclohexane/ethyl acetate, 4:1) to give the heptoside phosphate (0.25 g, 90%) as a colorless oil .MS-ESI (TOF-MS-ESI+) : m/z: 946 [M+Na]+.

Reference： [1]Current Patent Assignee: PHARMA OMNIUM INTERNATIONAL P O I - WO2012/73214, 2012, A2 Location in patent: Page/Page column 35

33
[ 1623-08-1 ]
[ 1378358-17-8 ]
[ 1378358-19-0 ]

Yield	Reaction Conditions	Operation in experiment
82%	With triethylamine; triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran at 20℃;	7.6 Step 6: l-Deoxy-2 , 3 , 4 , 6-tetra-0-benzyl-7-0- dibenzyloxyphosphoryl-D-glycero-D-manno-heptopyranoseTo a solution of the previous alcohol (32 mg, 0.061 mmol), PPh3 (80 mg, 0.305 mmol), (Bn)2P(0)OH (85 mg, 0.305 mmol), TEA (85 yL, 0.609 mmol) and THF (2 mL) , was slowly added DEAD (48 yL, 0.305 mmol) at room temperature and the mixture was stirred overnight. Then, the solvent was removed and the crude purified by silica gel chromatography (elution with ethyl acetate/cyclohexane, 4/6) to give the desired compound (40 mg, 82 % yield) . MS (ESI+) m/z 846.32 [M+Na]+: 100%.

Reference： [1]Current Patent Assignee: PHARMA OMNIUM INTERNATIONAL P O I - WO2012/73214, 2012, A2 Location in patent: Page/Page column 46

34
[ 1623-08-1 ]
[ 1378358-32-7 ]
[ 1378358-35-0 ]

Yield	Reaction Conditions	Operation in experiment
98%	With triethylamine; triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran at 20℃; for 96h;	8.5 Step 5: l-Deoxy-l-allyl-2 , 3 , 4 , 6-tetra-0-benzyl-7-0- dibenzyloxyphosphoryl-D-glycero-a-D-manno-heptopyranose and l-Deoxy-l-allyl-2 ,3,4, 6-tetra-0-benzyl-7- dibenzyloxyphosphoryl-D-glycero-p-D-manno-heptopyranoseTo a solution of previous a or β-anomers (0.082 mmol) , PPh3 (0.421 mmol), (BnO)2P(0)OH (0.402 mmol), TEA (0.842 mmol) and THF (2 mL) , was slowly added DEAD (0.421 mmol) at room temperature and the mixture was stirred for 4 days. Then, the solvent was removed and the residual crude purified by silica gel chromatography (elution with ethyl acetate/cyclohexane, 40/60) to provide the desired compounds . l-Deoxy-l-allyl-2, 3, 4, 6-tetra-0-benzyl-7-0- dibenzyloxyphosphoryl--glycero-oi-D-marmo-heptopyranose (70 mg, 98 % yield)MS (ESI+) m/z 877 [M+Na]+: 100%.l-Deoxy-l-allyl-2, 3, 4, 6-tetra-0-benzyl-7- dibenzyloxyphosphoryl-D-glycero^-D-ifiarmo-heptopyranose (30 mg, 70 % yield) .MS (ESI+ ) m/z 877 [M+Na] + : 100%.

Reference： [1]Current Patent Assignee: PHARMA OMNIUM INTERNATIONAL P O I - WO2012/73214, 2012, A2 Location in patent: Page/Page column 51-52

35
[ 1623-08-1 ]
[ 1378358-34-9 ]
[ 1378358-36-1 ]

Yield	Reaction Conditions	Operation in experiment
70%	With triethylamine; triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran at 20℃; for 96h;	9.5 Step 5: l-Deoxy-l-allyl-2 , 3 , 4 , 6-tetra-0-benzyl-7-0- dibenzyloxyphosphoryl-D-glycero-a-D-manno-heptopyranose and l-Deoxy-l-allyl-2 ,3,4, 6-tetra-0-benzyl-7- dibenzyloxyphosphoryl-D-glycero-p-D-manno-heptopyranoseTo a solution of previous a or β-anomers (0.082 mmol) , PPh3 (0.421 mmol), (BnO)2P(0)OH (0.402 mmol), TEA (0.842 mmol) and THF (2 mL) , was slowly added DEAD (0.421 mmol) at room temperature and the mixture was stirred for 4 days. Then, the solvent was removed and the residual crude purified by silica gel chromatography (elution with ethyl acetate/cyclohexane, 40/60) to provide the desired compounds . l-Deoxy-l-allyl-2, 3, 4, 6-tetra-0-benzyl-7-0- dibenzyloxyphosphoryl--glycero-oi-D-marmo-heptopyranose (70 mg, 98 % yield)MS (ESI+) m/z 877 [M+Na]+: 100%.l-Deoxy-l-allyl-2, 3, 4, 6-tetra-0-benzyl-7- dibenzyloxyphosphoryl-D-glycero^-D-ifiarmo-heptopyranose (30 mg, 70 % yield) .MS (ESI+ ) m/z 877 [M+Na] + : 100%.

Reference： [1]Current Patent Assignee: PHARMA OMNIUM INTERNATIONAL P O I - WO2012/73214, 2012, A2 Location in patent: Page/Page column 52

36
[ 1623-08-1 ]
[ 1394842-69-3 ]
[ 1394842-71-7 ]

Yield	Reaction Conditions	Operation in experiment
49%	With N-iodo-succinimide In tetrahydrofuran at 20℃; for 1h;	3 Step 3 157 mg (8R,9S,13S,14S,17S)-2-methoxy-13-methyl-3-((methylthio)methoxy)-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-yl acetate (0.39 mmol), 325 mg dibenzyl hydrogen phosphate (1.16 mmol, 3 eqv.), and 320 mg N-iodosuccinimide (1.42 mmol, 3.6 eqv.) were dissolved in 5-mL of dry tetrahydrofuran at room temperature. The reaction was stirred one hour after which time the solvent was removed in vacuo and the resulting solid was dissolved in a 1:2 v/v mixture of ethyl acetate and hexanes and the major product isolated with elution on a silica gel column with gradient elution (1:2 v/v ethyl acetate:hexanes to 1:1 v/v ethyl acetate:hexanes; Rf=0.62) to provide 120 mg (8R,9S,13S,14S,17S)-3-(((bis(benzyloxy)phosphoryl)oxy)methoxy)-2-methoxy-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-yl acetate (49% yield).

Reference： [1]Current Patent Assignee: UNIVERSITY OF KANSAS - US2012/225849, 2012, A1 Location in patent: Page/Page column 4

37
[ 1415481-52-5 ]
[ 108549-23-1 ]
[ 1623-08-1 ]
[ 1415481-53-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: biphenyl-4-yl 2,4,6-tri-O-benzoyl-α-D-mannopyranoside; Dibenzyl N,N-diisopropylphosphoramidite With 1,2,4-Triazole In acetonitrile at 0 - 20℃; for 24.3333h; Stage #2: With tert.-butylhydroperoxide In acetonitrile at 0 - 20℃; for 1h;	23 To a mixture of 26 (21 1 mg, 0.335 mmol) and 1 ,2,4-triazole (92.5 mg, 1 .34 mmol) in dry acetonitrile (5.0 mL) was added dibenzyl Λ/,/V-diisopropylphosphoramidite (90%) (0.25 mL, 0.67 mmol) at 0°C. The reaction mixture was stirred at 0°C for 20 min and further stirred at rt under argon for 24 h. Then ie f-butylhydroperoxide (190 μ, 1.34 mmol) was added to the reaction mixture at 0°C and the solution was stirred vigorously at rt for 1 h. The mixture was quenched with 1 M aq. Na2S203 and 1 M aq. NaHC03, and then extracted with DCM. The combined organic phases were washed with brine and dried over Na2S04. The solvent was removed under reduced pressure and the residue was purified by flash chromatography on silica gel (petrol ether/EtOAc 6:1 -4:1 ) to afford a mixture of 2- dibenzylphosphate and 27 (3:2, by NMR) (245 mg, 80%) as white solid.1H NMR (CDCI3, 500 MHz): δ 4.62 (m, 2H, H-5, H-6a), 4.76 (dd, J = 12.0, 7.5 Hz, 1 H, H- 6b), 4.85-5.1 1 (m, 4H, OCH2Ph), 5.55 (td, J = 3.5, 9.0 Hz, 1 H, H-3), 5.81 (d, J = 1 .5 Hz, 1 H, H-1 ), 5.87 {dd, J = 1 .9, 3.4 Hz, 1 H, H-2), 6.04 (m, 1 H, H-4), 6.92-8.1 1 (m, 34 H, Ar-H); 13C NMR (CDCI3, 125 MHz) δ 62.76 (C-5), 67.58 (d, J = 5.63 Hz, C-4), 69.51 (C-6), 69.75 (d, J = 5.63 Hz, OCH2Ph), 69.81 (d, J = 6.0 Hz, OCH2Ph), 70.95 (d, J = 2.0 Hz, C-2), 73.69 (d, J = 5.13 Hz, C-3), 95.69 (C-1 ), 1 16.82, 126.82, 127.55, 127.67, 127.85, 127.96, 128.20, 128.23, 128.27, 128.32, 128.41 , 128.50, 128.54, 128.57, 128.62, 129.71 , 129.85, 129.99, 132.99, 133.48, 133.64, 136.09, 140.35, 155.08 (Ar-C), 165.35, 165.46, 166.01 (3 CO); ESI-MS calcd for C53H45NaOi2P [M+Na]+: 927.25, found: 927.23.

Reference： [1]Current Patent Assignee: UNIVERSITY OF BASEL - WO2012/164074, 2012, A1 Location in patent: Page/Page column 45

38
[ 1623-08-1 ]
[ 50651-75-7 ]

Yield	Reaction Conditions	Operation in experiment
82.5%	With silver nitrate; sodium hydroxide In water Cooling with ice;	[00249] A. Synthesis of silver dibenzyl phosphate [00250] Dibenzyl phosphate (2.78 g, 10 mmol) in water (40 ml_) was cooled in an ice bath. Subsequently, 1 N NaOH was added while shaking the flask until the pH of solution was about 7. The solid dissolved almost completely. Then silver nitrate (1 .89 g, 1 1 mmol) in water (20 ml_) was added slowly. After adding, the resulting solid was collected by filtration and washed with water. The solid was dried in vacuum over phosphorus pentoxide to yield silver dibenzyl phosphate (3.18 g) (yield, 82.5%) as a white solid.

Reference： [1]Current Patent Assignee: KEMPHARM INC - WO2013/16668, 2013, A2 Location in patent: Paragraph 00249; 00250

39
[ 1623-08-1 ]
[ 1527527-16-7 ]
O-(2,3-di-O-benzyl-4,6-O-benzylidene-β-D-mannopyranosyl)-(1→2)-O-(3-O-benzyl-4,6-O-benzylidene-β-D-mannopyranosyl)-(1→2)-3-O-benzyl-4,6-O-benzylidene-D-mannopyranosyl dibenzylphosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	With N-iodo-succinimide; trifluorormethanesulfonic acid In dichloromethane at -20 - 0℃; for 1h; Inert atmosphere; Molecular sieve;	6 Method 1: To a solution of 13 (40 mg, 1 equiv) in dry CH2Cl2 underargon was added 1H-tetrazole (9.3 mg, 3.8 equiv) after whichthe reaction mixture was cooled down to 0 C. Dibenzyl(N,N-diisopropyl)phosphoramidite (30 lL, 2.5 equiv) was added after whichthe reaction mixture was allowed to warm up to room temperatureand was stirred for 22 h. The reaction mixture was then cooled to60 C and 20 mg m-CPBA was added. The reaction mixture wasstirred at 0 C for 1.5 h and at room temperature for 2 h after whichit was diluted with 40 mL CH2Cl2, washed with 2 15 mL of a saturatedsolution of Na2S2O3 in H2O, 2 15 mL of a saturated solutionof NaHCO3 in H2O and 2 10 mL H2O. The organic layer waspurified by column chromatography (hexane/EtOAc 1:1, Rf = 0.57)to yield 14 as a white foam. Yield of a-product: 20 mg (41%).a24D 51.7 (c 1.0 CH2Cl2).Method 2: To a solution of 9 (140 mg, 1 equiv) in 3 mL dry CH2-Cl2 under argon was added HOPO(OBn)2 (94.3 mg, 3 equiv) and 4 Åmolecular sieves. The reaction mixture was cooled to 20 C andNIS (30.5 mg, 1.2 equiv) and TfOH, (2.5 lL, 0.12 equiv) were added.The reaction mixture was stirred at 0 C for 1 h after which the reaction was quenched by adding 0.5 mL pyridine. The reactionmixture was diluted with 20 mL CH2Cl2 and washed with2 15 mL of a saturated solution of Na2S2O3 in H2O, 2 15 mLof a saturated solution of NaHCO3 in H2O and 1 15 mL H2O.The organic layer was dried over Na2SO4 and the solvent wasremoved. The crude product was purified by column chromatography(hexane/EtOAc 1:1) to yield 14 as a white foam. Yield ofa-product: 64.2 mg (42%). 1H NMR (600.13 MHz, CDCl3, 25C):d = 7.60-7.00 (m, 45H, arom. H), 5.60 (s, 1H, 4,6-OCH00Ph), 5.58(dd, 1H, JH-1,H-2 = 1.5 Hz, JH-1,P = 6.2 Hz, H-1), 5.45 (s, 1H, 4,6-OCH0Ph), 5.33 (s, 1H, 4,6-OCHPh), 5.08 and 5.03 [each dd, each,1H, J = 11.9 Hz, JCH2a,P = 8.9 Hz, JCH2b,P = 8.2 Hz, PO(OCH2Ph)],5.02 and 4.99 [each dd, each, 1H, J = 11.8 Hz, JCH2a,P = 13.6 Hz,JCH2b,P = 9.6 Hz, PO(OCH2Ph)], 5.00 (d, 1H, JH-100,H-200 = 0.1 Hz, H-100),4.91 and 4.69 (each d, each 1H, J = 12.5 Hz, 200-OCH2Ph), 4.83and 4.78 (each d, each 1H, J = 12.5 Hz, 30-OCH2Ph), 4.60 and4.56 (each d, each 1H, J = 12.2 Hz, 3-OCH2Ph), 4.47 (s, 1H, H-10),4.45 and 4.42 (each d, each 1H, J = 11.7 Hz, 300-OCH2Ph), 4.39(dd, 1H, JH-200,H-300 = 3.2 Hz, H-200), 4.34 (dd, 1H, JH-600a,H-500 = 4.8 Hz,JH-600a,H-600b = 10.4 Hz, H-600a), 4.29 (d, 1H, JH-20,H030 = 3.1 Hz, H-20),4.26 (dd, 1H, JH-60a,H-50 = 4.8 Hz, JH-60a,H-60b = 10.2 Hz, H-60a), 4.22(dd, 1H, JH-400,500 = 9.2 Hz, JH-400,H-300 = 9.8 Hz, H-400), 4.15 (dd, 1H, JH-2,H-3 = 3.3 Hz, H-2), 4.02 (dd, 1H, JH-40,H-50 = 9.4 Hz, JH-40,H-30 = 9.7 Hz, H-40), 3.99 (dd, 1H, JH-6a,H-5 = 4.9 Hz, JH-6a,H-6b = 10.3 Hz, H-6a), 3.97 (dd, 1H, JH-600b,500 = 10.2 Hz, H-600b), 3.85(dd, 1H, JH-4,H-5 = 9.0 Hz, JH-4,H-3 = 10.2 Hz, H-4), 3.84 (ddd, 1H, JH-5,H-6b = 10.1 Hz, H-5), 3.83 (dd, 1H, H-3), 3.67 (dd, 1H, JH-60b,H-50 = 10.1 Hz, H-60b), 3.60 (dd, 1H, H-6b), 3.59 (dd, 1H, H-30), 3.53(dd, 1H, -300), 3.41 (ddd, 1H, H-500), 3.24 (ddd, 1H, H-500) ppm. 13C NMR (150.9 MHz, CDCl3, 25 C): d = 139.3-135.2(arom. C),103.0 (C-100), 101.9 (4,6-OC0HPh), 101.6 (4,6-OCHPh), 101.3 (4,6-OC00HPh), 99.6 (C-10), 95.7 (2JC-1,P = 5.7 Hz, C-1), 79.2 (C-300), 78.1(C-4, C-40 , C-400), 76.2 (C-20), 76.0 (C-200), 75.5 (C-30), 74.9 (2-OCH2-Ph), 73.7 (3JC-2,P = 9.9 Hz, C-2), 73.5 (C-3), 72.1 (300-OCH2Ph), 71.9(3-OCH2Ph), 71.1 (30-OCH2Ph), 69.9 [2JC,P = 6.1 Hz, PO(OCH2Ph)],69.8 (2JC,P = 6.1 Hz, PO(OCH2Ph)], 68.7 (C-600), 68.5 (C-60), 68.3 (C-6), 67.9 (C-500), 67.6 (C-50), 65.5 (C-5) ppm.1JC-1,H-1 = 176.4 Hz (a), 1JC-10,H-10 = 156.2 Hz (b), 1JC-100,H-100 = 158.6 Hz (b).31P NMR (242.9 MHz, CDCl3, 25 C): d = 2.88 ppm.HRMS: m/z Calcd for C81H81O19PNa [M+Na]+: 1411.5007. Found1411.5025.

Reference： [1]Rahkila, Jani; Ekholm, Filip S.; Panchadhayee, Rajib; Arda, Ana; Canada, Francisco Javier; Jimenez-Barbero, Jesus; Leino, Reko [Carbohydrate Research, 2014, vol. 383, p. 58 - 68]

40
[ 1623-08-1 ]
[ 1527527-27-0 ]
O-(2,3-di-O-benzyl-4,6-O-benzylidene-β-D-mannopyranosyl)-(1→2)-O-(3-O-benzyl-4,6-O-benzylidene-β-D-mannopyranosyl)-(1→2)-O-(3-O-benzyl-4,6-O-benzylidene-β-D-mannopyranosyl)-(1→2)-3-O-benzyl-4,6-O-benzylidene-D-mannopyranosyl dibenzylphosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
47%	With N-iodo-succinimide; trimethylsilyl trifluoromethanesulfonate In dichloromethane at -50 - -20℃; for 22h; Inert atmosphere; Molecular sieve;	6 4.12 O-(2,3-Di-O-benzyl-4,6-O-benzylidene-β-d-mannopyranosyl)-(1→2)-O-(3-O-benzyl-4,6-O-benzylidene-β-d-mannopyranosyl)-(1→2)-O-(3-O-benzyl-4,6-O-benzylidene-β-d-mannopyranosyl)-(1→2)-3-O-benzyl-4,6-O-benzylidene-d-mannopyranosyl dibenzylphosphate (16) Method 1: To a solution of 15 (35 mg, 1 equiv) in 4 mL dry CH2Cl2 under argon was added 1H-tetrazole (6.3 mg, 3.8 equiv) after which the solution was cooled down to 0 °C. Dibenzyl(N,N-diisopropyl) phosphoramidite (22 μL, 2.5 equiv) was added and the reaction mixture was allowed to return to room temperature and was stirred for 2 h. The reaction mixture was cooled down to -60 °C and m-CPBA (13.5 mg, 3.8 equiv) was added and the mixture was stirred at 0 °C for 1 h and then at room temperature for 1 h. The reaction mixture was diluted with 50 mL CH2Cl2 and washed with 2 * 15 mL of a saturated solution of Na2S2O3 in H2O, 2 * 15 mL of a saturated solution of NaHCO3 in H2O and 2 * 10 mL H2O after which the organic layer was dried over NasSO4 and concentrated to dryness. The crude product was purified by column chromatography (hexane/EtOAc 1:1, Rf = 0.57) Yield of α-product: 25 mg (60%). -61.2° (c 1.0 CH2Cl2). Method 2: To a solution of 12 (50 mg, 1 equiv) in 3 mL dry CH2Cl2 under argon was added PO(OBn)2Oh (26.7 mg, 3 equiv) and 4 Å molecular sieves. The reaction mixture was cooled down to -50 °C and NIS (8.6 mg, 1.2 equiv) and TMSOTf (0.7 μL, 0.12 equiv) were added. The reaction mixture was stirred at -50 °C for 1 h and warmed to -20 °C and stirred for 3.5 h after which additional TMSOTf (0.7 μL, 0.12 equiv) was added and the reaction mixture was stirred for another 17.5 h at -20 °C. The reaction was quenched by adding 0.5 mL pyridine after which the reaction mixture was diluted with 20 mL CH2Cl2 and washed with 2 * 15 mL of a saturated solution of Na2S2O3 in H2O, 2 * 15 mL of a saturated solution of NaHCO3 in H2O and 1 * 15 mL H2O. The organic layer was dried over Na2SO4 and evaporated to dryness. The crude product was purified by column chromatography (hexane/EtOAc 1:1). Yield of α-product: 26 mg (47%). 1H NMR (600.13 MHz, CDCl3, 25 °C): δ = 7.75-6.75 (m, 55H, arom. H), 5.59 (dd, 1H, JH-1,H-2 = 1.7 Hz, JH-1,P = 6.3 Hz, H-1), 5.56 (s, 1H, 4,6-OCH‴Ph), 5.43 (s, 1H, 4,6-OCHPh), 5.41 (s and s, 2H, 4,6-OCH'Ph and 4,6-OCH"Ph), 5.14 (d, 1H, JH-1",H-2" = 0.1 Hz, H-1"), 5.08 and 5.02 [each dd, each, 1H, J = -11.9 Hz, JCH2a,P = 9.1 Hz, JCH2b,P = 8.2 Hz, PO(OCH2Ph)], 5.06 (d, 1H, JH-1‴,H-2‴ = 0.1 Hz, H-1‴), 5.01 and 4.98 [each dd, each, 1H, J = -11.6 Hz, JCH2a,P = 8.4 Hz, JCH2b,P = 9.9 Hz, PO(OCH2Ph)], 4.99 and 4.83 (each d, each 1H, J = -12.5 Hz, 2‴-OCH2Ph), 4.70 and 4.63 (each d, each 1H, J = -12.4 Hz, 3'-OCH2Ph), 4.65 and 4.50 (each d, each 1H, J = -11.9 Hz, 3"-OCH2Ph), 4.64 and 4.61 (each d, each 1H, J = -12.4 Hz, 3-OCH2Ph), 4.51 (dd, JH-2",H-3" = 3.1 Hz, H-2"), 4.50 (d, 1H, JH-1',H-2' = H-1'), 4.50 and 4.38 (each d, each 1H, J = -11.8 Hz, 3‴-OCH2Ph), 4.42 (dd, 1H, JH-2',H-3' = 3.3 Hz, H-2'), 4.39 (dd, 1H, JH-2‴,H-3‴ = 3.1 Hz, H-2‴), 4.36 (dd, 1H, JH-6"a,H-5" = 4.6 Hz, JH-6"a,H-6"b = -10.2 Hz, H-6"a), 4.26 (dd, 1H, JH-6'a,H-5' = 4.8 Hz, JH-6'a,H-6'b = -10.2 Hz, H-6'a), 4.18 (dd, 1H, JH-4‴,H-5‴ = 9.2 Hz, JH-4‴,H-3‴ = 9.9 Hz, H-4‴), 4.17 (dd, 1H, JH-6‴a,H-5‴ = 4.8 Hz, JH-6‴a,H-6‴b = -10.4 Hz, H-6‴a), 4.10 (dd, 1H, JH-2,H-3 = 3.7 Hz, H-2), 4.07 (dd, 1H, JH-4",H-5" = 9.3 Hz, JH-4",H-3" = 9.8 Hz, H-4"), 3.98 (dd, 1H, JH-6a,H-5 = 4.9 Hz, JH-6a,H-6b = -10.3 Hz, H-6a), 3.88 (dd, 1H, JH-4',H-5' = 9.4 Hz, JH-4',H-3' = 9.9 Hz, H-4'), 3.85 (dd and dd, 2H, JH-6‴b,H-5‴ = 10.1 Hz, JH-4,H-5 = 9.5 Hz, JH-4,H-3 = 10.1 Hz, H-6‴b and H-4), 3.82 (ddd, 1H, JH-5,H-6b = 10.3 Hz, H-5), 3.80 (dd, 1H, H-3), 3.78 (dd, 1H, JH-6"b,H-5" = 10.0 Hz, H-6''b), 3.73 (dd, 1H, JH-6'b,H-5' = 10.0 Hz, H-6'b), 3.62 (dd, 1H, H-3'), 3.55 (dd, 1H, H-6b), 3.53 (dd, 1H, H-3"), 3.52 (dd, 1H, H-3‴), 3.40 (ddd, 1H, H-5"), 3.31 (ddd, 1H, H-5‴), 3.27 (ddd, 1H, H-5') ppm. 13C NMR (150.9 MHz, CDCl3, 25 °C): δ = 139.4-126.1 (arom. C), 103.3 (C-1‴), 101.9 (C-1", 4,6-OCHPh, 4,6-OC'HPh), 101.5 (4,6-OC"HPh), 101.2 (4,6-OC'''HPh), 100.5 (C-1'), 95.7 (2JC-1,P = 4.9 Hz, C-1), 79.0 (C-3‴), 78.4 (C-4‴), 78.3 (C-4'), 71.2 (C-4, C-4"), 76.8 (C-3"), 76.2 (C-2"), 76.1 (C-3'), 75.9 (C-2‴), 74.9 (3JC-2,P = 9.3 Hz, C-2), 74.6 (2‴-OCH2Ph), 74.2 (C-2'), 73.4 (C-3), 72.2 (3‴-OCH2Ph), 72.1 (3-OCH2Ph), 71.3 (3'-OCH2Ph), 70.8 (3"-OCH2Ph), 69.9 [2JC,P = 5.4 Hz, 2JC,P = 5.8 Hz, PO(OCaH2Ph),PO(OCbH2Ph)], 68.8 (C-6"), 68.7 (C-6‴), 68.6 (C-6'), 68.3 (C-6), 68.0 (C-5"), 67.7 (C-5'), 67.5 (C-5‴), 65.5 (C-5) ppm.

Reference： [1]Rahkila, Jani; Ekholm, Filip S.; Panchadhayee, Rajib; Arda, Ana; Canada, Francisco Javier; Jimenez-Barbero, Jesus; Leino, Reko [Carbohydrate Research, 2014, vol. 383, p. 58 - 68]

41
[ 4753-59-7 ]
[ 1623-08-1 ]
[ 1383382-43-1 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: phosphoric acid dibenzyl ester With tetramethyl ammoniumhydroxide In methanol; water; acetone at -10℃; Stage #2: 4-Bromobutyl acetate In 1,4-dioxane for 5h; Reflux;	4 To a freshly prepared mixture of dibenzylphosphate/acetone (2), a mixture of tetramethylammonium hydroxide/methanol/water (1) was added dropwise at -10 C. Solvents were evaporated under a nitrogen stream. A 33% HBr solution in acetic acid was added to tetrahydrofuran (14). After 1 hour stirring at room temperature, solvents were evaporated under a gentle nitrogen stream. The pure 4-bromobutyl acetate (15) has been obtained. Tetramethylammonium dibenzylphosphate (3) was added to a solution of 4-bromobutyl acetate (15) in dioxane. The mixture was refluxed for 5 hours and dichloromethane was added. The reaction mixture was washed with water and dried with MgSO4. Volatiles were removed and the resulting crude product dibenzyl 4-acetatebutyl phosphate (16) was purified on silica.

Reference： [1]Current Patent Assignee: GOVERNMENT OF THE NETHERLANDS - US2014/17797, 2014, A1 Location in patent: Paragraph 0151-0154

42
[ 1623-08-1 ]
[ 1401341-69-2 ]
[ 1401341-72-7 ]

Yield	Reaction Conditions	Operation in experiment
71%	With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 20℃; for 2h;	14 Preparation of Compound 14 35 mg (0.07 mmol) of Compound 11 of Example 11, 29 mg (0.11 mmol) of triphenylphosphine, 23 µl (0.11 mmol) of DIAD, and 31 mg (0.11 mmol) of dibenzyl phosphate were added to 1 mL of trihydrofuran at room temperature, and the resulting solution was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure and then separated by column chromatography to obtain 40 mg (0.05 mmol) of Compound 14 as a white solid (yield: 71%). [0258] 1H NMR (600 MHz, CDCl3) δ 8.49 (s, 1H), 7.88 (d, J = 8.4Hz, 1H), 7.86 (s, 1H), 7.58 (dd, J1 = 12.6 Hz, J2 = 2.4 Hz, 1H), 7.43 (dd, J1 = 8.4 Hz, J2 = 8.4 Hz, 1H), 7.35 (m, 11H), 6.94 (d, J = 7.8 Hz, 1H), 6.00 (t, J = 6.0 Hz, 1H), 5.18 (m, 4H), 5.11 (d, J1 = 11.4 Hz, 1H), 4.82 (m, 1H), 4.11 (dd, J1 = 9.0 Hz, J2 = 9.0 Hz, 1H), 4.06 (t, J = 5.4 Hz, 2H), 3.90 (s, 2H), 3.82 (dd, J1 = 9.0 Hz, J2 = 7.2 Hz, 1H), 3.74 (m, 1H), 3.66 (m, 1H), 2.04 (s, 3H) [0259] LCMS: 741(M+H+) for C36H36FN6O8P
71%	With di-isopropyl azodicarboxylate; triphenylphosphine at 20℃; for 2h;	14 Preparation of Compound 14 35 mg (0.07 mmol) of Compound 11 of Example 11, 29 mg (0.11 mmol) of triphenylphosphine, 23 μl (0.11 mmol) of DIAD, and 31 mg (0.11 mmol) of dibenzyl phosphate were added to 1 mL of trihydrofuran at room temperature, and the resulting solution was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure and then separated by column chromatography to obtain 40 mg (0.05 mmol) of Compound 14 as a white solid (yield: 71%). [0270] 1H NMR (600 MHz, CDCl3) δ 8.49 (s, 1H), 7.88 (d, J=8.4 Hz, 1H), 7.86 (s, 1H), 7.58 (dd, J1=12.6 Hz, J2=2.4 Hz, 1H), 7.43 (dd, J1=8.4 Hz, J2=8.4 Hz, 1H), 7.35 (m, 11H), 6.94 (d, J=7.8 Hz, 1H), 6.00 (t, J=6.0 Hz, 1H), 5.18 (m, 4H), 5.11 (d, J1=11.4 Hz, 1H), 4.82 (m, 1H), 4.11 (dd, J1=9.0 Hz, J2=9.0 Hz, 1H), 4.06 (t, J=5.4 Hz, 2H), 3.90 (s, 2H), 3.82 (dd, J1=9.0 Hz, J2=7.2 Hz, 1H), 3.74 (m, 1H), 3.66 (m, 1H), 2.04 (s, 3H) [0271] LCMS: 741(M+H+) for C36H36FN6O8P

Reference： [1]Current Patent Assignee: LEGOCHEM BIOSCIENCES INC. - EP2692727, 2014, A2 Location in patent: Paragraph 0257-0259
[2]Current Patent Assignee: LEGOCHEM BIOSCIENCES INC. - US2014/179691, 2014, A1 Location in patent: Paragraph 0268-0271

43
[ 53008-65-4 ]
[ 1623-08-1 ]
C₃₀H₂₇Cl₃N₄O₇ [ No CAS ]
methyl 6-O-[2-O-(2-azidomethylbenzoyl)-3-O-benzyl-4,6-O-benzylidene-α-D-mannopyranosyl]-2,3,4-tri-O-benzyl-α-D-glucopyranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With trimethylsilyl trifluoromethanesulfonate In dichloromethane at -78℃; for 2h; Molecular sieve; Inert atmosphere;	1 3.2. Glycosylation of the primary alcohol 9 in the presence of diphenyl phosphonate (10) A mixture of imidate 3b (52.6mg, 79.4μmol), alcohol 9 (36.9mg, 79.4μmol), dibenzyl phosphate (10) (22.1mg, 79.4μmol) and pulverized activated MS4A (80mg) in dry CH2Cl2 (1.60mL) was stirred at room temperature for 1h under argon to remove a trace amount of water. Then the reaction mixture was cooled to -78°C. To the reaction mixture was added TMSOTf (17.3μL, 95.3μmol, 1.2equiv) at the same temperature. After being stirred at -78°C for 2h, the reaction mixture was neutralized with NEt3 and filtered through a pad of Celite. The filtrate was concentrated in vacuo. The residue was purified by a column chromatography on silica gel with 85:15 hexane:ethyl acetate to give 11 (52.4mg, 54.4mmol, 68%, α only), 70:30 hexane:ethyl acetate to give 12 (trace). 3.2.1 Methyl 6-O-[2-O-(2-azidomethylbenzoyl)-3-O-benzyl-4,6-O-benzylidene-α-d-mannopyranosyl]-2,3,4-tri-O-benzyl-α-d-glucopyranoside (11) [α]21D[α]D21 +16.5 (c 1.24, CHCl3); 1H NMR (400MHz, CDCl3) δ 8.06 (dd, 1H, J=1.4, 7.8Hz), 7.15-7.62 (m, 27H), 5.64 (s, 1H), 5.58 (dd, 1H, J=1.4, 3.4Hz), 4.98-5.04 (d, 2H, J=10.7Hz), 4.89 (d, 1H, J=11.2Hz), 4.68-4.84 (m, 7H), 4.64 (d, 1H, J=3.4Hz), 4.52 (d, 1H, J=11.2Hz), 4.21 (dd, 1H, J=4.4, 9.8Hz), 4.13 (t, 1H, J=9.3, 9.8Hz), 4.05 (dd, J=3.4, 9.8Hz), 4.01 (dd, 1H, J=9.3, 9.8Hz), 3.66-3.95 (m, 5H), 3.58 (dd, 1H, J=3.4, 9.8Hz), 3.44 (dd, 1H, J=9.2, 9.3Hz), 3.33 (s, 3H); 13C NMR (100MHz, CDCl3) δ 165.7, 138.9, 138.1, 138.0, 137.8, 137.5, 137.2, 132.9, 131.4, 129.8, 128.9, 128.8, 128.4×3, 128.3, 128.2, 128.1, 128.0, 127.9, 127.8, 127.7, 127.6, 126.1, 101.7, 98.8, 97.8, 82.0, 80.1, 78.8, 77.6, 77.2, 75.7, 75.0, 73.3, 72.1, 70.6, 69.8, 68.8, 66.5, 64.0, 55.1, 52.9; IR (KBr) 3065, 3032, 2927, 2103, 1723, 1497, 1454, 1370, 1256, 1157, 1132, 1091, 1028, 915, 739, 698 (cm-1); HRMS (ESI-TOF) Calcd for C56H61N4O12 [M+NH4] FontWeight="Bold" FontSize="10" 981.4286, found 981.4232. 3.2.2 Dibenzylphospholyl 2-O-(2-azidomethylbenzoyl)-3-O-benzyl-4,6-O-benzylidene-α-d-mannopyranoside (12) [α]21D[α]D21 -8.39 (c 0.640, CHCl3); 1H NMR (400MHz, CDCl3) δ 8.10 (d, 1H), 7.20-7.62 (m, 23H), 5.75 (dd, 1H, J=1.5, 6.4Hz), 5.60 (s, 1H), 5.52 (dd, 1H, J=1.4, 3.4Hz), 5.04-5.15 (m, 4H), 4.73 (s, 2H), 4.67 (s, 2H), 3.91-4.15 (m, 4H), 3.76 (t, 1H, J=9.8, 10.2Hz); 31P NMR (100MHz, CDCl3) δ -2.27; IR (KBr) 2930, 2103, 1726, 1579, 1497, 1456, 1374, 1255, 1159, 1092, 1016, 927, 745, 697 (cm-1); HRMS (ESI-TOF) Calcd for C42H44N4O10P [MNH4] FontWeight="Bold" FontSize="10" 795.2795, found 795.2789.

Reference： [1]Ohira, Shuichi; Yamaguchi, Yoshiki; Takahashi, Takashi; Tanaka, Hiroshi [Tetrahedron, 2015, vol. 71, # 37, p. 6602 - 6611]

44
[ 1623-08-1 ]
silver nitrate [ No CAS ]
[ 50651-75-7 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: phosphoric acid dibenzyl ester With sodium hydroxide In water at 20℃; for 0.5h; Stage #2: silver nitrate In water
83%	Stage #1: phosphoric acid dibenzyl ester With sodium hydroxide In ethanol; water for 0.0833333h; Stage #2: silver nitrate In ethanol; water for 0.25h;	3.3 Silver dibenzyl phosphate 3 Dibenzyl phosphate silver salt was synthesized according to thepublished procedure [41]. Briefly, dibenzyl phosphate (1.00 g,3.59 mmol) was dissolved in ethanol/water mixture (50/50 V/V,10 mL). The solution of sodium hydroxide (3.59 mL, 1.00 M,3.59mmol)was added and the solution stirred for 5min. Then silver nitrate(610mg, 3.59mmol) dissolved in hotwater (5.0 mL)was added. Acolorless precipitatewas formed immediately. After 15 min the suspensionwas suction filtered and the precipitate washed with cold water(5.0 mL) and ethanol (5.0 mL) and dried in vacuo to yield colorlesssolid (1.15 g, 3.00 mmol, 83% yield). 1H NMR (300 MHz, DMSO-d6) δ7.32-7.20 (m, 10H), 4.74 (s, 2H), 4.72 (s, 2H). 13C NMR (75 MHz,DMSO-d6) δ 140.07, 139.96, 128.73, 127.75, 66.88, 66.80. LRMS, ESI:m/z 277.0 [M - H]-, 555.3 [2M - H]-, 833.7 [3M - H]-.
82.5%	Stage #1: phosphoric acid dibenzyl ester With sodium hydroxide In water Cooling with ice; Stage #2: silver nitrate In water	A A. Synthesis of Silver Dibenzyl Phosphate: A. Synthesis of Silver Dibenzyl Phosphate: (0284) Dibenzyl phosphate (2.78 g, 10 mmol) in water (40 mL) was cooled in an ice bath. Subsequently, 1N NaOH was added while shaking the flask until the pH of solution was about 7. The solid dissolved almost completely. Then silver nitrate (1.89 g, 11 mmol) in water (20 mL) was added slowly. After adding, the resulting solid was collected by filtration and washed with water. The solid was dried in vacuum over phosphorus pentoxide to yield silver dibenzyl phosphate (3.18 g) (yield, 82.5%) as a white solid.

75%	Stage #1: phosphoric acid dibenzyl ester With sodium carbonate In water for 0.5h; Stage #2: silver nitrate In water for 0.5h; Darkness;
34.1 g	Stage #1: phosphoric acid dibenzyl ester With sodium hydroxide In water at 20℃; for 0.5h; Stage #2: silver nitrate In water	11.11C Example 11C: silver (1 +) dibenzyl phosphate Dibenzyl hydrogen phosphate (26.7 g, 96 mmol) was suspended in 300 mL of deionized water, and sodium hydroxide (1 M aqueous, 96 mL, 96 mmol) solution was added.The resulting suspension was stirred at room temperature for 30 minutes, at which point a complete dissolution resulted and a pH of ~6-7 was achieved. A separate solution of silver(I) nitrate (17.12 g, 101 mmol) in 150 mL of water was added dropwise via addition funnel while stirring vigorously. The resulting white solid was isolated by filtration through a 600-mL fritted funnel. The isolated solid was washed with acetone (2 c 200 mL) and methyl tert- butyl ether (200 mL) and then was dried to constant weight in a vacuum oven at 70 °C to give 34.1 g of the title compound as a white solid, which was used without additional purification orcharacterization.

Reference： [1]Randolph, John T.; Voight, Eric A.; Greszler, Stephen N.; Uno, Brice E.; Newton, James N.; Gleason, Kenneth M.; Stolarik, DeAnne; Van Handel, Cecilia; Bow, Daniel A. J.; Degoey, David A. [Journal of Medicinal Chemistry, 2020, vol. 63, # 19, p. 11034 - 11044]
[2]Babič, Andrej; Herceg, Viktorija; Ateb, Imène; Allémann, Eric; Lange, Norbert [Journal of Controlled Release, 2016, vol. 235, p. 155 - 164]
[3]Current Patent Assignee: KEMPHARM INC - US2015/266911, 2015, A1 Location in patent: Paragraph 0284
[4]Hoshiya, Naoyuki; Takenaka, Kei; Shuto, Satoshi; Uenishi, Jun'ichi [Organic Letters, 2016, vol. 18, # 1, p. 48 - 51]
[5]Current Patent Assignee: GOOGLE INC - WO2020/77217, 2020, A1 Location in patent: Paragraph 00276; 00278

45
[ 1623-08-1 ]
[ 2444-46-4 ]
C₃₁H₄₀NO₆P [ No CAS ]

Reference： [1]ACS Chemical Biology,2015,vol. 10,p. 2884 - 2890

46
[ 1623-08-1 ]
[ 458-37-7 ]
dibenzyl 4-[(1E,6E)-7-(4-hydroxy-3-methoxyphenyl)-3,5-dioxohepta-1,6-dien-1-yl]-2-methoxyphenyl phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20%	With dmap; N-ethyl-N,N-diisopropylamine In tetrachloromethane; ethyl acetate at -25℃; for 8h; Inert atmosphere;	Dibenzyl 4-((1E,6E)-7-(4-hydroxy-3-methoxyphenyl)-3,5-dioxohepta-1,6-dienyl)-2-methoxyphenyl phosphate (1) To a solution of curcumin (0.3 g, 0.81 mmol), CCl4 (0.78 mL, 8.10 mmol), DIPEA (0.44 g, 3.42 mmol) and DMAP (19.90 mg, 0.16 mmol) in anhydrous ethyl acetate (30 mL), dibenzyl phosphate (0.641 g, 2.44 mmol) was added dropwise at 25 °C under a N2 atmosphere. The resulting homogeneous mixture was stirred for 8 h at 25 °C and evaporated to dryness under reduced pressure. The residue was diluted to 100 mL with ethyl acetate, successively washed with water (3 x 100 mL) and brine (3 x 100 mL), and dried over anhydrous Na2SO4. After filtration, the filtrate was evaporated under reduced pressure to give crude product, which was purified by silica gel chromatography to give yellow oil (0.1 g, 20 %). 1H-NMR (600 MHz, DMSO-d6) δ: 9.74 (s, 1H), 7.60 (d, J = 6.2 Hz, 1H), 7.58 (d, J = 6.2 Hz, 1H), 7.50 (s, 1H), 7.46-7.35 (m, 10H), 7.34 (d, J = 5.2 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 7.23(d, J = 8.3 Hz, 1H), 7.17 (d, J = 8.1 Hz, 1H), 6.95 (d, J = 15.9 Hz, 1H), 6.83 (d, J = 8.1 Hz, 1H), 6.80 (d,J = 15.8 Hz, 1H), 6.12 (d, J = 8.6 Hz, 1H), 5.19 (d, J = 8.1 Hz, 4H), 3.85 (d, J = 10.4 Hz, 6H); 13C-NMR (150MHz, DMSO-d6) δ: 185.3, 181.8, 151.1, 149.9, 148.4, 142.0, 140.8, 139.3, 136.2, 133.4, 128.9 (5C), 128.7,128.3 (5C), 127.9, 126.6, 124.9, 123.8, 121.8, 121.6, 116.1, 112.8, 111.8, 101.8, 69.8 (2C), 56.5, 56.1; ESI-MS[M - H]- m/z: 627.5.

Reference： [1]Ding, Luyang; Ma, Shuli; Lou, Hongxiang; Sun, Longru; Ji, Mei [Molecules, 2015, vol. 20, # 12, p. 21501 - 21514]

47
[ 1623-08-1 ]
[ 458-37-7 ]
dibenzyl 4,4'-((1E,6E)-3,5-dioxohepta-1,6-diene-1,7-diyl)bis(2-methoxy-4,1-phenylene) diphosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
39%	With dmap; N-ethyl-N,N-diisopropylamine In tetrachloromethane; ethyl acetate at -25℃; for 8h; Inert atmosphere;	Dibenzyl 4-((1E,6E)-7-(4-hydroxy-3-methoxyphenyl)-3,5-dioxohepta-1,6-dienyl)-2-methoxyphenyl phosphate (1) General procedure: To a solution of curcumin (0.3 g, 0.81 mmol), CCl4 (0.78 mL, 8.10 mmol), DIPEA (0.44 g, 3.42 mmol) and DMAP (19.90 mg, 0.16 mmol) in anhydrous ethyl acetate (30 mL), dibenzyl phosphate (0.641 g, 2.44 mmol) was added dropwise at 25 °C under a N2 atmosphere. The resulting homogeneous mixture was stirred for 8 h at 25 °C and evaporated to dryness under reduced pressure. The residue was diluted to 100 mL with ethyl acetate, successively washed with water (3 x 100 mL) and brine (3 x 100 mL), and dried over anhydrous Na2SO4. After filtration, the filtrate was evaporated under reduced pressure to give crude product, which was purified by silica gel chromatography to give yellow oil (0.1 g, 20 %).

Reference： [1]Ding, Luyang; Ma, Shuli; Lou, Hongxiang; Sun, Longru; Ji, Mei [Molecules, 2015, vol. 20, # 12, p. 21501 - 21514]

48
[ 1623-08-1 ]
methyl (tolyl 2,3,4-tri-O-acetyl-1-thio-α-D-mannopyranosyluronate) [ No CAS ]
methyl 2,3,4-tri-O-acetyl-α-D-mannopyranosyluronate dibenzyl 1-phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With N-iodo-succinimide; trifluorormethanesulfonic acid In dichloromethane at 0℃; for 1h; stereoselective reaction;	4.2. General experimental procedure for synthesis of D-mannopyranosyluronate dibenzylphosphate 16, 17 and 18 General procedure: After coevaporation with toluene three times, the thioglycosidedonor 10, 11 or 15 (2 mmol) and dibenzylphosphate (4 mmol) weredissolved in dry DCM (9 ml). NIS (3 mmol) and TfOH (0.28 mmol)were added to the reaction solution at 0 C, the mixture was stirredfor 1 h and monitored by TLC analysis. The reaction mixture wasquenched by the addition of 5% aq.Na2S2O3-solution (30 ml). Theaqueous layer was separated and extracted with DCM. The combinedorganic layers were dried over Na2SO4 and the solvent wasremoved in vacuo. Purification by column chromatograpy (silica gel,pentane/DCM/EtOAc, 3/1/1, v/v/v) yielded 16, 17 or 18.

Reference： [1]Zhang, Qingju; Howell, P.Lynne; Overkleeft, Herman S.; Filippov, Dmitri V.; van der Marel, Gijsbert A.; Codée, Jeroen D.C. [Carbohydrate Research, 2017, vol. 450, p. 12 - 18]

49
[ 1623-08-1 ]
methyl (tolyl 2,3-di-O-acetyl-4-deoxy-1-thio-α-D-mannopyranosyluronate) [ No CAS ]
(methyl 2,3-di-O-acetyl-4-deoxy-α-D-mannopyranosyluronate)dibenzylphosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With N-iodo-succinimide; trifluorormethanesulfonic acid In dichloromethane at 0℃; for 1h; stereoselective reaction;	4.2. General experimental procedure for synthesis of D-mannopyranosyluronate dibenzylphosphate 16, 17 and 18 General procedure: After coevaporation with toluene three times, the thioglycosidedonor 10, 11 or 15 (2 mmol) and dibenzylphosphate (4 mmol) weredissolved in dry DCM (9 ml). NIS (3 mmol) and TfOH (0.28 mmol)were added to the reaction solution at 0 C, the mixture was stirredfor 1 h and monitored by TLC analysis. The reaction mixture wasquenched by the addition of 5% aq.Na2S2O3-solution (30 ml). Theaqueous layer was separated and extracted with DCM. The combinedorganic layers were dried over Na2SO4 and the solvent wasremoved in vacuo. Purification by column chromatograpy (silica gel,pentane/DCM/EtOAc, 3/1/1, v/v/v) yielded 16, 17 or 18.

Reference： [1]Zhang, Qingju; Howell, P.Lynne; Overkleeft, Herman S.; Filippov, Dmitri V.; van der Marel, Gijsbert A.; Codée, Jeroen D.C. [Carbohydrate Research, 2017, vol. 450, p. 12 - 18]

50
[ 1623-08-1 ]
methyl (tolyl 2,3-di-O-acetyl-4-O-methyl-1-thio-α-D-mannopyranosyluronate) [ No CAS ]
(methyl 2,3-di-O-acetyl-4-O-methyl-α-D-mannopyranosyluronate)dibenzylphosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With N-iodo-succinimide; trifluorormethanesulfonic acid In dichloromethane at 0℃; for 1h; stereoselective reaction;	4.2. General experimental procedure for synthesis of D-mannopyranosyluronate dibenzylphosphate 16, 17 and 18 General procedure: After coevaporation with toluene three times, the thioglycosidedonor 10, 11 or 15 (2 mmol) and dibenzylphosphate (4 mmol) weredissolved in dry DCM (9 ml). NIS (3 mmol) and TfOH (0.28 mmol)were added to the reaction solution at 0 C, the mixture was stirredfor 1 h and monitored by TLC analysis. The reaction mixture wasquenched by the addition of 5% aq.Na2S2O3-solution (30 ml). Theaqueous layer was separated and extracted with DCM. The combinedorganic layers were dried over Na2SO4 and the solvent wasremoved in vacuo. Purification by column chromatograpy (silica gel,pentane/DCM/EtOAc, 3/1/1, v/v/v) yielded 16, 17 or 18.

Reference： [1]Zhang, Qingju; Howell, P.Lynne; Overkleeft, Herman S.; Filippov, Dmitri V.; van der Marel, Gijsbert A.; Codée, Jeroen D.C. [Carbohydrate Research, 2017, vol. 450, p. 12 - 18]

51
[ 1196-57-2 ]
[ 1623-08-1 ]
dibenzyl (3-oxo-3,4-dihydroquinoxalin-2-yl)phosphonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With dipotassium peroxodisulfate In acetonitrile at 100℃; for 8h;	6 Dibenzyl (3-oxo-3,4-dihydroquinoxalin-2-yl) phosphonate A solution of quinoxaline-2 (1H) -one, 0.2 mmol of dibenzyl phosphate, 0.6 mmol of potassium persulfate,2.0 mL, added to 10 mL of the reaction tube, placed in an oil bath at 100 ° C and reacted under air for 8 h. Stop the reaction and cool to roomtemperature. The reaction solution was spin-dried with a rotary evaporator,70.0 mg of the desired product was isolated by column chromatography in a yield of 80%.

Reference： [1]Current Patent Assignee: HUAQIAO UNIVERSITY - CN105037425, 2017, B Location in patent: Paragraph 0036; 0037; 0038

52
[ 944711-16-4 ]
[ 1623-08-1 ]
C₃₅H₃₅O₉P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With dmap; N-ethyl-N,N-diisopropylamine In tetrachloromethane; acetonitrile at -10℃; for 2h; Inert atmosphere;	1 Preparation of compound (IIa) N2, 10 mL of acetonitrile was added to 370 mg (1 mmol) of Ia,Cooled to -10 ° C, 770 mg (5 mmol) of CCl4,0.38 mL (2.1 mmol) of N, N-diisopropylethylamine was added over 30 minAnd 0.4 mg (1.4 mmol) of dibenzyl phosphite were added dropwise over 30 min. After incubation for 1 h, 4 mL of 0.5 mol / L KH2PO4 solution was added,Stirring at room temperature for 5 min, dropping acetonitrile under reduced pressure,Add 5 mL of water, extracted with ethyl acetate, concentrated,The residue was stirred with 15 mL of petroleum ether, Precipitation of white solid,To give compound IIa,Yield 95%.

Reference： [1]Current Patent Assignee: SHIJIAZHUANG UNIVERSITY - CN106883267, 2017, A Location in patent: Paragraph 0011; 0012

53
[ 108-78-1 ]
[ 1623-08-1 ]
C₁₄H₁₅O₄P*C₃H₆N₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	In water at 72℃; for 5h;	13 Example 13 At room temperature, 27.8 g (0.1 mol) of ditolyl phosphate was added to 100 ml of water, and while stirring, 12.6 g(0.1mol) melamine to mix well, then heated to 72 reaction 5h, cooled to room temperature, filtered to remove the water was whiteSolid, drying, is the final product. Yield 99%.

Reference： [1]Current Patent Assignee: SICHUAN UNIVERSITY - CN107163076, 2017, A Location in patent: Paragraph 0049; 0050

54
[ 1623-08-1 ]
[ 645-93-2 ]
C₃H₄N₄O₂*C₁₄H₁₅O₄P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	In water at 90℃; for 6h;	14 Example 14 At room temperature, 27.8 g (0.1 mol) of ditolyl phosphate was added to 100 ml of water, and while stirring, 12.8 g(0.1mol) 2-amino-4,6-dihydroxy s-triazine to mix well, then heated to 90 reaction 6h, cooled to room temperature, overThe water was removed by filtration to give a white solid which was dried to give the final product. Yield 98%.

Reference： [1]Current Patent Assignee: SICHUAN UNIVERSITY - CN107163076, 2017, A Location in patent: Paragraph 0051; 0052; 0055; 0056

55
[ 1623-08-1 ]
[ 645-92-1 ]
C₁₄H₁₅O₄P*C₃H₅N₅O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	In water at 85℃; for 8h;	15 Example 15 At room temperature, 27.8 g (0.1 mol) of ditolyl phosphate was added to 100 ml of water, and while stirring, 12.7 g(0.1mol) 4,6-diamino-2-hydroxy-1,3,5-triazine to mix well, then heated to 85 reaction 8h, cooled to roomTemperature, filtered off water to a white solid, drying, is the final product. Yield 97%.

Reference： [1]Current Patent Assignee: SICHUAN UNIVERSITY - CN107163076, 2017, A Location in patent: Paragraph 0053; 0054

56
[ 1623-08-1 ]
N-(2,6-dimethoxypyridin-3-yl)-N-(2-hydroxyethyl)-9-methyl-9H-carbazole-3-sulfonamide [ No CAS ]
dibenzyl (2-((N-(2,6-dimethoxypyridin-3-yl)-9-methyl-9H-carbazole)-3-sulfonamido)ethyl)phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	Stage #1: phosphoric acid dibenzyl ester With N-chlorophthalimide In toluene at 20℃; for 2h; Stage #2: N-(2,6-dimethoxypyridin-3-yl)-N-(2-hydroxyethyl)-9-methyl-9H-carbazole-3-sulfonamide In pyridine; toluene at 0 - 20℃; for 5h;	20.1 Synthesis step (1): dibenzyl-2-N-(2,6-dimethoxypyridin-3-yl)-9-Methyl-3-carbazolesulfonamide ethyl phosphate (33) Dibenzyl phosphite (0.52 g, 2.0 mmol) was dissolved in 5.0 mL anhydrous toluene at 0°CChlorobenzosuccinimide (0.32 g, 2.4 mmol) was added and stirred for 2 h at room temperature before use.Dissolve N-(2,6-dimethoxypyridin-3-yl)-N-(2-hydroxyethyl)-9-methyl-3-carbazolesulfonamide (31, 0.22 g, 0.45 mmol) In 5.0 mL dry pyridine.At 0°C, the newly prepared dibenzyl phosphate solution was filtered into the pyridine reaction solution, gradually warmed to room temperature for 5 hours, and the reaction was complete by TLC.Extracted with methylene chloride, washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated.Column chromatography (PE/AcOEt=2/1) was isolated and purified to give an oil (0.18 g, yield 57%).

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES - CN107382967, 2017, A Location in patent: Paragraph 0161; 0162; 0163

57
[ 1623-08-1 ]
[ 343309-52-4 ]
dibenzyl (2,2-diphenyl-2H-chromen-4-yl) phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	In 1,2-dichloro-ethane at 80℃; for 3h;	General procedure for the preparation of product 2H-chromen-4-yl phosphinates/phosphonates 3, 4, and 5: General procedure: The mixture of 2-propynolphenols 1 (0.1 mmol) and R2P(O)OH (0.2 mmol) was stirred in DCE or 1,4-dioxane (2.0 mL) at 80°C under air. After 3.0 h, the completion of the reaction was monitored by TLC. Then, the solvent was concentrated and the residue was purified by flash chromatography on silica gel to afford the desired products. 2
85%	In 1,2-dichloro-ethane at 80℃; for 3h;	2 Example 2: Preparation of dibenzyl (2,2-diphenyl-2H-chromen-4-yl) phosphate Add o-propargyl phenol-2 (300 mg, 1 mmol) and 5 ml of dry 1,2-dichloroethane to the reaction flask at room temperature, then add dibenzyl phosphate (556 mg, 2 mmol). Into the reaction flask, then place the reaction at 80 °C After 3 hours of reaction, TLC followed the progress of the reaction. The separation and purification steps were the same as in Example 1 dibenzyl (2,2-diphenyl-2H-chromen-4-yl) phosphate obtain 476 mg, reaction yield 85%

Reference： [1]Zhang, Yuxing; Song, Xian-Rong; Jin, Fengyan; Yang, Tao; Yang, Ruchun; Xiao, Qiang [Tetrahedron Letters, 2021, vol. 65]
[2]Current Patent Assignee: JIANGXI SCIENCE & TECHNOLOGY NORMAL UNIVERSITY - CN109824725, 2019, A Location in patent: Paragraph 0015

58
[ 162883-52-5 ]
[ 1623-08-1 ]
C₃₆H₄₉O₆P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With triethylamine In tetrahydrofuran at 80℃; for 3h;	2 Referring to Route 4, bis-sodium 2-((3R,8R,10S,13S,14S,17S)-3-hydroxy-3,10,13-trimethylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)-2-oxoethyl phosphate. The mixture of 2l-bromo-ganaxolone (0.82 g, 1.99 mmol), dibenzyl phosphate (1.66 g, 3 eq.) and trimethylamine (0.83 mL, 3.3 eq.) in 26 mL of THF was heated at 80 °C for 3h. It was cooled and was concentrated. Biotage purification (10-80% EtOAc in hexane) afforded the desired product (0.675 g, 56% yield). LCMS (M+l, 609.38). 1HNMR (400 MHz, Chloroform- d3) d 7.41 - 7.27 (m, 10H), 5.21 - 4.98 (m, 4H), 4.57 - 4.32 (m, 2H), 2.44 (t, J = 8.8 Hz, 1H), 2.15 (q, J = 11.6, 10.7 Hz, 1H), 1.81 (d, J = 9.0 Hz, 1H), 1.66 (dd, J = 11.4, 6.0 Hz, 3H), 1.52 (d, J = 18.7 Hz, 7H), 1.42 - 1.22 (m, 3H), 1.20 (d, J = 1.4 Hz, 3H), 1.18 - 1.01 (m, 1H), 0.94 (qd, J = 11.7, 11.2, 5.0 Hz, 1H), 0.83 - 0.75 (m, 1H), 0.74 (s, 3H), 0.59 (s, 3H).

Reference： [1]Current Patent Assignee: TEXAS A&M UNIVERSITY SYSTEM - WO2019/209850, 2019, A1 Location in patent: Paragraph 0103; 0117

59
[ 100-42-5 ]
[ 1623-08-1 ]
dibenzyl (2-iodo-1-phenylethyl) phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With N-iodo-succinimide In tetrahydrofuran at 40℃; for 12h; Inert atmosphere;	21 Example 21 Preparation of dibenzyl (2-iodo-1-phenylethyl) phosphate 0.5 mmol of dibenzyloxyphosphinic acid,0.5 mmol of styrene and 0.6 mmol of N-iodosuccinimide were added to the Schlenk tube under nitrogen.Add 1.0 mL of tetrahydrofuran under a nitrogen atmosphere and stir the reaction at 40 oC for 12 hours.After the reaction is completed, the target product can be obtained in 75% yield by column chromatography.
75%	With N-iodo-succinimide In tetrahydrofuran at 40℃; for 6h; Inert atmosphere; regioselective reaction;

Reference： [1]Current Patent Assignee: HUNAN INSTITUTE OF SCIENCE AND TECH - CN110590835, 2019, A Location in patent: Paragraph 0035
[2]Xiong, Biquan; Xu, Shipan; Zhu, Yu; Yao, Lei; Zhou, Congshan; Liu, Yu; Tang, Ke-Wen; Wong, Wai-Yeung [Chemistry - A European Journal, 2020, vol. 26, # 43, p. 9556 - 9560]

60
[ 1623-08-1 ]
N-(2,6-dimethoxypyridine-3-yl)-7-hydroxy-9-methyl-3-carbazole-3-sulfonamide [ No CAS ]
dibenzyl (6-(N-(2,6-dimethoxypyridin-3-yl)sulfamoyl)-9-methyl-9H-carbazol-2-yl)phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	Stage #1: N-(2,6-dimethoxypyridine-3-yl)-7-hydroxy-9-methyl-3-carbazole-3-sulfonamide With dmap; carbon tetrabromide; N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; for 0.5h; Inert atmosphere; Stage #2: phosphoric acid dibenzyl ester In dichloromethane at 20℃; for 4h; Inert atmosphere;	4.1.19 Dibenzyl (6-(N-(2,6-dimethoxypyridin-3-yl)sulfamoyl)-9-methyl-9H-carbazol-2-yl) phosphate (12) To a solution of compound 4b (200mg, 0.48mmol) in dried DCM (10.0mL) was added N-ethyldiisopropylamine (0.20mL, 1.2mmol), carbon tetrabromide (647mg, 1.93mmol), and 4-dimethylaminopyridine (5.8mg, 0.05mmol) at 0°C and the mixture solution was stirred for 30min on an ice-water bath. Then dibenzyl phosphite (250mg, 0.96mmol) was added in the solution. The reaction mixture was then allowed to warm to room temperature and stirred for 4h. The solvent was diluted with DCM (50mL) and washed consecutively with 5% sodium dihydrogen phosphate solution (15mL), brine (25mL), dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified on silica gel using Petroleumether (60-90°C)/ethyl acetate (2:1) to afford 274mg (89%) of 12 as an oily matter. 1HNMR (DMSO-d6, 400MHz) δ ppm 3.42 (3H, s), 3.73 (3H, s), 3.84 (3H, s), 5.23 (4H, d, J=8.4Hz), 6.30 (1H, d, J=8.4Hz), 7.11-7.14 (1H, m), 7.34-7.41 (10H, m), 7.43 (2H, m), 7.74 (2H, m), 8.24 (1H, d, J=8.4Hz), 8.47 (1H, s), 9.35 (1H, s); 13CNMR (DMSO-d6, 101MHz) δ ppm 29.4, 39.5, 52.9, 53.3, 54.9, 69.4, 69.49, 100.6, 101.5, 101.6, 109.2, 112.1, 112.5, 118.9, 119.7, 120.8, 121.79, 124.2, 128.0, 128.4, 130.9, 135.6, 135.7, 139.4, 141.9, 142.8, 149.3, 149.4, 156.8, 160.2; 31PNMR (DMSO-d6, 162MHz) δ ppm-6.18; HRMS (ESI+): m/z calcd for C34H33O8N3PS [M+H]+: 674.1755; found: 674.1720.

Reference： [1]Gu, Yuxi; Hu, Laixing; Liu, Yonghua; Sun, lianqi; Wu, Yanbin [European Journal of Medicinal Chemistry, 2020, vol. 191]

61
[ 1623-08-1 ]
C₃₁H₃₉Cl₂NO₁₃S [ No CAS ]
C₃₉H₄₈Cl₂NO₁₇P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	Stage #1: phosphoric acid dibenzyl ester; C₃₁H₃₉Cl₂NO₁₃S In dichloromethane at -20℃; for 1h; Molecular sieve; Stage #2: With trifluorormethanesulfonic acid In dichloromethane at -20℃; for 4h;	6 That is, first, 3 Å molecular sieve (540 mg) and NIS (122 mg, 542 μmol) were added to compound 14 (200 mg, 271 μmol).And dibenzyl phosphate (189 mg, 678 μmol)Was added to a solution of CH2Cl2 (5.4 mL) at ambient temperature. After stirring at -20 ° C. for 1 hour, TfOH (trifluoromethanesulfonic acid) (2.4 μL, 27 μmol) was added to the mixture at -20 ° C. The reaction mixture was stirred at -20 ° C. for 4 hours while monitoring the reaction with TLC (n-hexane / AcOEt = 3: 2).The reaction mixture was then quenched with saturated aqueous NaHCO3 solution, filtered through a Celite pad and the pad washed with CHCl3. The filtrate and the washing liquid were combined, washed with saturated aqueous Na2S2O3 solution and brine, dried over Na2SO4, and concentrated. The obtained residue was purified by silica gel column chromatography using n-hexane / acetone (2.7: 1) as an eluent to obtain Compound 15 (yield 242 mg, yield 99%).

Reference： [1]Current Patent Assignee: TOKAI NATIONAL HIGHER EDUCATION AND RESEARCH SYSTEM - JP2020/158489, 2020, A Location in patent: Paragraph 0187-0192

62
[ 1623-08-1 ]
C₁₉H₁₃FO₂S [ No CAS ]
dibenzyl (2-(4-fluorophenyl)-2-(thiophen-2-yl)-2H-chromen-4-yl) phosphate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	In 1,2-dichloro-ethane at 80℃; for 3h;	General procedure for the preparation of product 2H-chromen-4-yl phosphinates/phosphonates 3, 4, and 5: General procedure: The mixture of 2-propynolphenols 1 (0.1 mmol) and R2P(O)OH (0.2 mmol) was stirred in DCE or 1,4-dioxane (2.0 mL) at 80°C under air. After 3.0 h, the completion of the reaction was monitored by TLC. Then, the solvent was concentrated and the residue was purified by flash chromatography on silica gel to afford the desired products. 2