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【结 构 式】

【分子编号】34974

【品名】methyl 7-[(allyloxy)methyl]naphtho[2,3-d][1,3]dioxole-6-carboxylate

【CA登记号】

【 分 子 式 】C17H16O5

【 分 子 量 】300.31104

【元素组成】C 67.99% H 5.37% O 26.64%

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:(XX)

The bromination of 7-methylnaphtho[2,3-d][1,3]benzodioxole-6-carboxylic acid methyl ester (XVII) with NBS and AIBN in refluxing CCl4 gives the bromomethyl derivative (XVIII), which is treated with allyl alcohol (XIX) and NaH in THF yielding the corresponding allyl ether (XIX). The condensation of (XIX) with the chiral auxiliary (XX) by means of triethylamine and pyridine in acetonitrile affords the oxazolidine (XXII), which is treated with (PPh3)3RhCl and 1,4-diazabicyclo[2.2.2]octane in refluxing propanol giving the carbinol (XXIII). The protection of (XXIII) with TBDMS-Cl, Et3N and DMAP provides the silyl ether (XXIV), which is arylated with 3,4,5-trimethoxyphenyllithium (XXV) in THF giving intermediate (XXVI). Opening of the oxazoline ring of (XXVI) with TFA and acetic anhydride yields the carboxylic ester (XXVII), which is treated with Ti(O-i-Pr)4 in hot ethanol to afford the lactone (XXVIII). The reaction of (XXVIII) with NaOH in methanol, methylation with diazomethane and silylation with TBDMS-Cl gives the carboxylic ester (XXIX), which is treated with NBS in DMSO/THF to afford the chiral bromohydrine (XXX). The debromination of (XXX) with Bu3SnH and AIBN in refluxing toluene provides the hydroxyester (XXXI).

1 Andrews, R.C.; et al.; Asymetric total synthesis of (-)-podophyllotoxin. J Am Chem Soc 1988, 110, 23, 7854.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XVII) 34972 methyl 7-methylnaphtho[2,3-d][1,3]dioxole-6-carboxylate C14H12O4 详情 详情
(XVIII) 34973 methyl 7-(bromomethyl)naphtho[2,3-d][1,3]dioxole-6-carboxylate C14H11BrO4 详情 详情
(XIX) 12234 2-Propen-1-ol; Allyl alcohol 107-18-6 C3H6O 详情 详情
(XX) 34974 methyl 7-[(allyloxy)methyl]naphtho[2,3-d][1,3]dioxole-6-carboxylate C17H16O5 详情 详情
(XXI) 34975 (2S,3R)-3-amino-4-methoxy-2-butanol C5H13NO2 详情 详情
(XXII) 34976 (4R,5R)-2-[7-[(allyloxy)methyl]naphtho[2,3-d][1,3]dioxol-6-yl]-4-(methoxymethyl)-5-methyl-4,5-dihydro-1,3-oxazole; allyl [7-[(4R,5R)-4-(methoxymethyl)-5-methyl-4,5-dihydro-1,3-oxazol-2-yl]naphtho[2,3-d][1,3]dioxol-6-yl]methyl ether C21H23NO5 详情 详情
(XXIII) 34977 [7-[(4R,5R)-4-(methoxymethyl)-5-methyl-4,5-dihydro-1,3-oxazol-2-yl]naphtho[2,3-d][1,3]dioxol-6-yl]methanol C18H19NO5 详情 详情
(XXIV) 34978 (4R,5R)-2-[7-([[tert-butyl(dimethyl)silyl]oxy]methyl)naphtho[2,3-d][1,3]dioxol-6-yl]-4-(methoxymethyl)-5-methyl-4,5-dihydro-1,3-oxazole; tert-butyl(dimethyl)silyl [7-[(4R,5R)-4-(methoxymethyl)-5-methyl-4,5-dihydro-1,3-oxazol-2-yl]naphtho[2,3-d][1,3]dioxol-6-yl]methyl ether C24H33NO5Si 详情 详情
(XXV) 34979 (3,4,5-trimethoxyphenyl)lithium C9H11LiO3 详情 详情
(XXVI) 34980 (4R,5R)-2-[(5R)-7-([[tert-butyl(dimethyl)silyl]oxy]methyl)-5-(3,4,5-trimethoxyphenyl)-5,6-dihydronaphtho[2,3-d][1,3]dioxol-6-yl]-4-(methoxymethyl)-5-methyl-4,5-dihydro-1,3-oxazole; tert-butyl(dimethyl)silyl [(8R)-7-[(4R,5R)-4-(methoxymethyl)-5-methyl-4,5-dihydro-1,3-oxazol-2-yl]-8-(3,4,5-trimethoxyphenyl)-7,8-dihydronaphtho[2,3-d][1,3]dioxol-6-yl]methyl ether C33H45NO8Si 详情 详情
(XXVII) 34981 (1R,2R)-2-(acetamido)-3-methoxy-1-methylpropyl (5R)-7-[(acetoxy)methyl]-5-(3,4,5-trimethoxyphenyl)-5,6-dihydronaphtho[2,3-d][1,3]dioxole-6-carboxylate C31H37NO11 详情 详情
(XXVIII) 34982 (5R)-5-(3,4,5-trimethoxyphenyl)-5,9-dihydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6(8H)-one C22H20O7 详情 详情
(XXIX) 34983 methyl (5R,6S)-7-([[tert-butyl(dimethyl)silyl]oxy]methyl)-5-(3,4,5-trimethoxyphenyl)-5,6-dihydronaphtho[2,3-d][1,3]dioxole-6-carboxylate C29H38O8Si 详情 详情
(XXX) 34984 methyl (5R,6R,7R)-7-bromo-7-([[tert-butyl(dimethyl)silyl]oxy]methyl)-8-hydroxy-5-(3,4,5-trimethoxyphenyl)-5,6,7,8-tetrahydronaphtho[2,3-d][1,3]dioxole-6-carboxylate C29H39BrO9Si 详情 详情
(XXXI) 34985 methyl (5R,6S,7S)-7-([[tert-butyl(dimethyl)silyl]oxy]methyl)-8-hydroxy-5-(3,4,5-trimethoxyphenyl)-5,6,7,8-tetrahydronaphtho[2,3-d][1,3]dioxole-6-carboxylate C29H40O9Si 详情 详情
Extended Information