(3R,4R,5R)-2-[(2,2,2-trichloroethanimidoyl)oxy]-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate -Drug Synthesis Database

【结构式】

【分子编号】48975

【品名】(3R,4R,5R)-2-[(2,2,2-trichloroethanimidoyl)oxy]-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate

【CA登记号】

【分子式】C₂₇H₄₄Cl₃NO₇Si₂

【分子量】657.178

【元素组成】C 49.35% H 6.75% Cl 16.18% N 2.13% O 17.04% Si 8.55%

与该中间体有关的原料药合成路线共 2 条

合成路线1 合成路线2

合成路线1

该中间体在本合成路线中的序号：(XIII)

Synthesis of intermediate monosaccharide (XIII): The reaction of D-xylose (VII) with benzyl alcohol and HCl (gas) gives the 1-O-benzyl-D-xylose (VIII), which is regioselectively acylated with 4-methoxybenzoyl chloride (IX) and pyridine to yield 1-O-benzyl-2-O-(4-methoxybenzoyl)-D-xylose (X). The silylation of (X) with Tes-Cl and imidazole in DMF affords the disilylated compound (XI), which is debenzylated by hydrogenation with H2 over Pd/C in ethyl acetate to provide 2-O-(4-methoxybenzoyl)-3,4-O-bis(triethylsilyl)-D-xylose (XII). Finally, this compound is converted into the target trichloroacetimidate (XIII) by reaction with trichloroacetonitrile and DBU in dichloromethane.

参考文献中间体

合成目标

【1】 Deng, S.; et al.; First total synthesis of an exceptionally potent antitumor saponin, OSW-1. J Org Chem 1999, 64, 1, 202.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
(VII)	48970	2,3,4,5-Tetrahydroxypentanal; D-xylopyranose; D-(+)-Xylose; D-xylose; D-(+)-Wood Sugar; Xylose; Wood Sugar	58-86-6	C₅H₁₀O₅	详情	详情
(VIII)	48971	(3R,4S,5R)-2-(benzyloxy)tetrahydro-2H-pyran-3,4,5-triol		C₁₂H₁₆O₅	详情	详情
(IX)	22671	4-Methoxybenzoyl chloride; p-Methoxybenzoyl chloride; 4-Anisoyl chloride	100-07-2	C₈H₇ClO₂	详情	详情
(X)	48972	(3R,4S,5R)-2-(benzyloxy)-4,5-dihydroxytetrahydro-2H-pyran-3-yl 4-methoxybenzoate		C₂₀H₂₂O₇	详情	详情
(XI)	48973	(3R,4R,5R)-2-(benzyloxy)-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate		C₃₂H₅₀O₇Si₂	详情	详情
(XII)	48974	(3R,4R,5R)-2-hydroxy-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate		C₂₅H₄₄O₇Si₂	详情	详情
(XIII)	48975	(3R,4R,5R)-2-[(2,2,2-trichloroethanimidoyl)oxy]-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate		C₂₇H₄₄Cl₃NO₇Si₂	详情	详情

合成路线2

该中间体在本合成路线中的序号：(XIII)

Synthesis of intermediate disaccharide (XVII): The regioselective glycosylation of intermediate arabinose derivative (VI) with the intermediate acetimidate (XIII) by means of BF3/Et2O gives the disaccharide (XIV), which is silylated with Tes-OTf and lutidine in dichloromethane to yield the fully protected disaccharide (XV). Elimination of the benzyl protecting group of (XV) by hydrogenation with H2 over Pd/C in hot ethyl acetate affords the hemiacetal (XVI), which is converted into the target trichloroacetimidate (XVII) by reaction with trichloroacetonitrile and DBU in dichloromethane.

参考文献中间体

合成目标

【1】 Deng, S.; et al.; First total synthesis of an exceptionally potent antitumor saponin, OSW-1. J Org Chem 1999, 64, 1, 202.

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(VI)	48969	(2S,3R,4S,5S)-2-(benzyloxy)-4,5-dihydroxytetrahydro-2H-pyran-3-yl acetate	C₁₄H₁₈O₆	详情	详情
(XIII)	48975	(3R,4R,5R)-2-[(2,2,2-trichloroethanimidoyl)oxy]-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₂₇H₄₄Cl₃NO₇Si₂	详情	详情
(XIV)	48976	(2S,3R,4R,5R)-2-[[(2S,3R,4S,5S)-3-(acetoxy)-2-(benzyloxy)-5-hydroxytetrahydro-2H-pyran-4-yl]oxy]-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₃₉H₆₀O₁₂Si₂	详情	详情
(XV)	48977	(2S,3R,4R,5R)-2-([(2S,3R,4R,5S)-3-(acetoxy)-2-(benzyloxy)-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-4-yl]oxy)-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₄₅H₇₄O₁₂Si₃	详情	详情
(XVI)	48978	(2S,3R,4R,5R)-2-([(3R,4R,5S)-3-(acetoxy)-2-hydroxy-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-4-yl]oxy)-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₃₈H₆₈O₁₂Si₃	详情	详情
(XVII)	48979	(2S,3R,4R,5R)-2-([(3R,4R,5S)-3-(acetoxy)-2-[(2,2,2-trichloroethanimidoyl)oxy]-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-4-yl]oxy)-4,5-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₄₀H₆₈Cl₃NO₁₂Si₃	详情	详情

Extended Information