(2S,3R,4R,5S)-4-hydroxy-2-(phenylsulfanyl)-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl acetate -Drug Synthesis Database

【结构式】

【分子编号】48942

【品名】(2S,3R,4R,5S)-4-hydroxy-2-(phenylsulfanyl)-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl acetate

【CA登记号】

【分子式】C₁₉H₃₀O₅SSi

【分子量】398.5957

【元素组成】C 57.25% H 7.59% O 20.07% S 8.04% Si 7.05%

与该中间体有关的原料药合成路线共 4 条

合成路线1 合成路线2 合成路线3 合成路线4

合成路线1

该中间体在本合成路线中的序号：(VIII)

Synthesis of intermediate monosaccharide (VIII): The reaction of the tetraacetyl-L-arabinose (I) with Ph-SH and SnCl4 gives the thioglycoside (II), which is deacetylated with NaOMe in methanol, yielding compound (III). The reaction of (III) with 2,2-dimethoxypropane (IV) and CSA in dichloromethane affords the acetonide (V), which is acetylated with Ac2O, DMAP and TEA to provide the acetate (VI). Elimination of the acetonide group of (VI) with Amberlite IR-118B furnishes diol (VII), which is selectively silylated with Tes-OTf and lutidine in dichloromethane to afford the desired intermediate monosaccharide (VIII).

参考文献中间体

合成目标

【1】 Jin, Z.; Yu, W.; A new strategy for the stereoselective introduction of steroid side chain via alpha-alkoxy vinyl cuprates: Total synthesis of a highly potent antitumor natural product OSW-1. J Am Chem Soc 2001, 123, 14, 3369.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
(I)	48936	D-Arabinose tetraacetate		C₁₃H₁₈O₉	详情	详情
(II)	48937	(2S,3R,4S,5S)-3,5-bis(acetoxy)-2-(phenylsulfanyl)tetrahydro-2H-pyran-4-yl acetate		C₁₇H₂₀O₇S	详情	详情
(III)	48938	(2S,3R,4S,5S)-2-(phenylsulfanyl)tetrahydro-2H-pyran-3,4,5-triol		C₁₁H₁₄O₄S	详情	详情
(IV)	10722	1-Methoxy-1-methylethyl methyl ether; 2,2-Dimethoxypropane	77-76-9	C₅H₁₂O₂	详情	详情
(V)	48939	(3aS,6S,7R,7aR)-2,2-dimethyl-6-(phenylsulfanyl)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-7-ol		C₁₄H₁₈O₄S	详情	详情
(VI)	48940	(3aS,6S,7R,7aS)-2,2-dimethyl-6-(phenylsulfanyl)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-7-yl acetate		C₁₆H₂₀O₅S	详情	详情
(VII)	48941	(2S,3R,4S,5S)-4,5-dihydroxy-2-(phenylsulfanyl)tetrahydro-2H-pyran-3-yl acetate		C₁₃H₁₆O₅S	详情	详情
(VIII)	48942	(2S,3R,4R,5S)-4-hydroxy-2-(phenylsulfanyl)-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl acetate		C₁₉H₃₀O₅SSi	详情	详情

合成路线2

该中间体在本合成路线中的序号：(VIII)

Synthesis of intermediate disaccharide (XX): The condensation of intermediate monosaccharide (VIII) with intermediate acetimidate (XVIII) by means of BF3/Et2O gives the disaccharide (XIX), which is converted into the desired acetimidate (XX) by reaction with NBS and trichloroacetonitrile and DBU in dichloromethane/water.

参考文献中间体

合成目标

【1】 Jin, Z.; Yu, W.; A new strategy for the stereoselective introduction of steroid side chain via alpha-alkoxy vinyl cuprates: Total synthesis of a highly potent antitumor natural product OSW-1. J Am Chem Soc 2001, 123, 14, 3369.

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(VIII)	48942	(2S,3R,4R,5S)-4-hydroxy-2-(phenylsulfanyl)-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl acetate	C₁₉H₃₀O₅SSi	详情	详情
(XVIII)	48950	(3R,4S,5R)-4,5-bis[(4-methoxybenzyl)oxy]-2-[(2,2,2-trichloroethanimidoyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₃₁H₃₂Cl₃NO₉	详情	详情
(XIX)	48951	(2S,3R,4S,5R)-2-([(2S,3R,4R,5S)-3-(acetoxy)-2-(phenylsulfanyl)-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-4-yl]oxy)-4,5-bis[(4-methoxybenzyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₄₈H₆₀O₁₃SSi	详情	详情
(XX)	48952	(2S,3R,4S,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[(4-methoxybenzyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₄₄H₅₆Cl₃NO₁₄Si	详情	详情

合成路线3

该中间体在本合成路线中的序号：(VIII)

. L- Arabinose monosaccharide intermediate (VIII): The reaction of tetraacetyl-L-arabinose (I) with Ph-SH by means of SnCl4 in dichloromethane gives the acetylated thioglycoside (II), which is deacetylated by means of NaOMe in methanol to yield thioglycoside (III). The reaction of (III) with 2,2-dimethoxypropane (IV) and CSA in dichloromethane affords the acetonide (V), which is acetylated with Ac2O, TEA and DMAP to provide monoacetate (VI). The cleavage of the acetonide group of (VI) by means of Amberlite IR-118H leads to the monoacetylated thioglycoside (VII), which is finally selectively monosilylated with Tms-OTf and lutidine in dichloromethane the target L-arabinose intermediate (VIII)

参考文献中间体

合成目标

【1】 Yu, W.; Jin, Z.; Total synthesis of the anticancer natural product OSW-1. J Am Chem Soc 2002, 124, 23, 6576.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
(I)	48936	D-Arabinose tetraacetate		C₁₃H₁₈O₉	详情	详情
(II)	48937	(2S,3R,4S,5S)-3,5-bis(acetoxy)-2-(phenylsulfanyl)tetrahydro-2H-pyran-4-yl acetate		C₁₇H₂₀O₇S	详情	详情
(III)	48938	(2S,3R,4S,5S)-2-(phenylsulfanyl)tetrahydro-2H-pyran-3,4,5-triol		C₁₁H₁₄O₄S	详情	详情
(IV)	10722	1-Methoxy-1-methylethyl methyl ether; 2,2-Dimethoxypropane	77-76-9	C₅H₁₂O₂	详情	详情
(V)	48939	(3aS,6S,7R,7aR)-2,2-dimethyl-6-(phenylsulfanyl)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-7-ol		C₁₄H₁₈O₄S	详情	详情
(VI)	48940	(3aS,6S,7R,7aS)-2,2-dimethyl-6-(phenylsulfanyl)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-7-yl acetate		C₁₆H₂₀O₅S	详情	详情
(VII)	48941	(2S,3R,4S,5S)-4,5-dihydroxy-2-(phenylsulfanyl)tetrahydro-2H-pyran-3-yl acetate		C₁₃H₁₆O₅S	详情	详情
(VIII)	48942	(2S,3R,4R,5S)-4-hydroxy-2-(phenylsulfanyl)-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl acetate		C₁₉H₃₀O₅SSi	详情	详情

合成路线4

该中间体在本合成路线中的序号：(VIII)

Intermediate beta-disaccharide trichloroacetimidate (XX): The glycosylation of intermediate (VIII) with intermediate (XVIII) by means of BF3/Et2O in dichloromethane gives the beta-disaccharide (XIX), which is converted into the target trichloroacetimidate (XX) by reaction with NBS, Cl3C-CN and DBU in dichloromethane

参考文献中间体

合成目标

【1】 Yu, W.; Jin, Z.; Total synthesis of the anticancer natural product OSW-1. J Am Chem Soc 2002, 124, 23, 6576.

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(VIII)	48942	(2S,3R,4R,5S)-4-hydroxy-2-(phenylsulfanyl)-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl acetate	C₁₉H₃₀O₅SSi	详情	详情
(XVIII)	48950	(3R,4S,5R)-4,5-bis[(4-methoxybenzyl)oxy]-2-[(2,2,2-trichloroethanimidoyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₃₁H₃₂Cl₃NO₉	详情	详情
(XIX)	48951	(2S,3R,4S,5R)-2-([(2S,3R,4R,5S)-3-(acetoxy)-2-(phenylsulfanyl)-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-4-yl]oxy)-4,5-bis[(4-methoxybenzyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₄₈H₆₀O₁₃SSi	详情	详情
(XX)	60151	(2S,3R,4S,5R)-2-({(2S,3R,4R,5S)-3-(acetyloxy)-2-[(2,2,2-trichloroethanimidoyl)oxy]-5-[(triethylsilyl)oxy]tetrahydro-2H-pyran-4-yl}oxy)-4,5-bis[(4-methoxybenzyl)oxy]tetrahydro-2H-pyran-3-yl 4-methoxybenzoate	C₄₄H₅₆Cl₃NO₁₄Si	详情	详情

Extended Information