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【结 构 式】

【分子编号】10527

【品名】(1S,5S,6R,7S,8S,10S,11S,13R)-7-[(acetoxy)methyl]-7,8,10-trihydroxy-11,15,18,18-tetramethyl-3,12-dioxo-2,4-dioxatetracyclo[12.3.1.0(1,5).0(6,11)]octadec-14-en-13-yl acetate

【CA登记号】

【 分 子 式 】C25H34O11

【 分 子 量 】510.53836

【元素组成】C 58.82% H 6.71% O 34.47%

与该中间体有关的原料药合成路线共 1 条

合成路线1

该中间体在本合成路线中的序号:(XVI)

Compound (XV) is selectively acetylated with acetic anhydride and DMAP to the diol (XVI). The replacement of the benzyl protecting group by a triethylsilyl (TES) group in (XVI) by debenzylation with H2 over Pd(OH)2/C followed by treatment with TESCl in pyridine and deacetylation with K2CO3 in methanol affords the silylated triol (XVII). The formation of the oxetane ring is carried out by treatment of (XVII) with trimethylsilyl chloride (TMSCl) and pyridine (silylation of the primary alcohol), subsequent reaction with Tf2O (activation of the secondary alcohol), and cyclization by acidic treatment with CSA to give compound (XVIII) with the oxetane ring and a tertiary OH group. The acetylation of (XVIII) with acetic anhydride and DMAP affords compound (XIX) with the tertiary acetoxy group. The reaction of (XIX) with phenyllithium gives the benzoyloxy derivative (XX), which is oxidized with pyridinium chlorochromate (PCC) to yield the diketone (XXI). The reduction of (XXI) with NaBH4 in methanol affords compound (XXII) with the appropriate secondary hydroxy group, which is acylated with Ojima's beta-lactam (XXIII) by means of sodium bis(trimethylsilyl)amide to give the silylated paclitaxel (XXIV). Finally, this compound is deprotected with HF/pyridine.

1 Yang, Z.; Liu, J.J.; Nicolaou, K.C.; et al.; Total synthesis of taxol. Nature 1994, 367, 6464, 630.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XV) 10526 (1S,5S,6R,7S,8S,10S,11S,13R)-7,8,10-trihydroxy-7-(hydroxymethyl)-11,15,18,18-tetramethyl-3,12-dioxo-2,4-dioxatetracyclo[12.3.1.0(1,5).0(6,11)]octadec-14-en-13-yl acetate C23H32O10 详情 详情
(XVI) 10527 (1S,5S,6R,7S,8S,10S,11S,13R)-7-[(acetoxy)methyl]-7,8,10-trihydroxy-11,15,18,18-tetramethyl-3,12-dioxo-2,4-dioxatetracyclo[12.3.1.0(1,5).0(6,11)]octadec-14-en-13-yl acetate C25H34O11 详情 详情
(XVII) 10528 (1S,5S,6R,7S,8S,10S,11S,13R)-7,8-dihydroxy-7-(hydroxymethyl)-11,15,18,18-tetramethyl-3,12-dioxo-10-[(triethylsilyl)oxy]-2,4-dioxatetracyclo[12.3.1.0(1,5).0(6,11)]octadec-14-en-13-yl acetate C29H46O10Si 详情 详情
(XVIII) 10529 (1S,5S,6R,7S,10R,12S,13S,15R)-7-hydroxy-13,17,20,20-tetramethyl-3,14-dioxo-12-[(triethylsilyl)oxy]-2,4,9-trioxapentacyclo[14.3.1.0(1,5).0(6,13).0(7,10)]icos-16-en-15-yl acetate C29H44O9Si 详情 详情
(XIX) 10530 (1S,5S,6R,10R,12S,13S,15R)-15-(acetoxy)-13,17,20,20-tetramethyl-3,14-dioxo-12-[(triethylsilyl)oxy]-2,4,9-trioxapentacyclo[14.3.1.0(1,5).0(6,13).0(7,10)]icos-16-en-7-yl acetate C31H46O10Si 详情 详情
(XX) 10531 (1S,2S,3R,4S,7R,9S,10S,12R)-4,12-bis(acetoxy)-1-hydroxy-10,14,17,17-tetramethyl-11-oxo-9-[(triethylsilyl)oxy]-6-oxatetracyclo[11.3.1.0(3,10).0(4,7)]heptadec-13-en-2-yl benzoate C37H52O10Si 详情 详情
(XXI) 10488 (1S,2S,3R,4S,7R,9S,10S,12R)-4,12-bis(acetoxy)-1-hydroxy-10,14,17,17-tetramethyl-11,15-dioxo-9-[(triethylsilyl)oxy]-6-oxatetracyclo[11.3.1.0(3,10).0(4,7)]heptadec-13-en-2-yl benzoate C37H50O11Si 详情 详情
(XXII) 10473 (1S,2S,3R,4S,7R,9S,10S,12R,15S)-4,12-bis(acetoxy)-1,15-dihydroxy-10,14,17,17-tetramethyl-11-oxo-9-[(triethylsilyl)oxy]-6-oxatetracyclo[11.3.1.0(3,10).0(4,7)]heptadec-13-en-2-yl benzoate C37H52O11Si 详情 详情
(XXIII) 10490 (3R,4S)-1-Benzoyl-4-phenyl-3-[(triethylsilyl)oxy]-2-azetanone C22H27NO3Si 详情 详情
(XXIV) 10535 (1S,2S,3R,4S,7R,9S,10S,12R,15S)-4,12-bis(acetoxy)-15-([(2R,3S)-3-(benzoylamino)-3-phenyl-2-[(triethylsilyl)oxy]propanoyl]oxy)-1-hydroxy-10,14,17,17-tetramethyl-11-oxo-9-[(triethylsilyl)oxy]-6-oxatetracyclo[11.3.1.0(3,10).0(4,7)]heptadec-13-en-2-yl benzoate n/a AB 详情 详情
Extended Information