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【结 构 式】

【分子编号】11202

【品名】(1R)-4-([(1S,5S,6R)-3-[(1R)-2-(Methoxymethoxy)-1-(2-methoxy-6-methylphenyl)ethyl]-8-methyl-2,4-dioxo-3,8-diazabicyclo[3.2.1]oct-6-yl]carbonyl)-10,10-dimethyl-3lambda(6)-thia-4-azatricyclo[5.2.1.0(1,5)]decane-3,3-dione

【CA登记号】

【 分 子 式 】C30H41N3O8S

【 分 子 量 】603.73696

【元素组成】C 59.68% H 6.84% N 6.96% O 21.2% S 5.31%

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:(IX)

An asymmetric synthesis of (-)-quinocarcin has been described: The acylation of 2-(2-methoxy-6-methylphenyl)-(R)- glycinol (I) with maleic anhydride (II) in ether gives the maleic monoamide (III), which is cyclized to the pyrrolidinedione (IV) by refluxing with acetic anhydride. The cyclization of (IV) with methyl azide in toluene affords the pyrrolotriazole (V), which is irradiated with UV light (Hg lamp), giving the aziridinopyrrole (VI). The cycloaddition of (VI) with the chiral acrylamide (VII) affords the diazabicyclo[3.2.1]octane (VIII). At this point, the hydroxyl group of (VIII) is protected with methoxymethyl chloride giving the methoxymethyl ether (IX), which is submitted to benzylic bromination with N-bromosuccinimide (NBS) in chloroform, yielding the bromo derivative (X). The reaction of (X) with triphenylphosphine affords the phosphonium salt (XI), which by treatment with potassium tert-butoxide and heat cyclizes to the tetracyclo compound (XII). Hydrogenation of (XII) with H2 over RaNi in ethanol affords the reduced compound (XIII), which is treated with LiOH in THF - water, affording the free acid derivative (XIV). The deprotection of the ether group of (XIV) with trimethylsilyl chloride and NaI in acetonitrile gives the hydroxymethyl derivative (XV), which is finally cyclized to (-)-quinocarcin with AgNO3 in methanol-water.

1 Ho, W.B.; Garner, P.; Shin, H.; Asymmetric synthesis of (-)-quinocarcin. J Am Chem Soc 1992, 114, 7, 2767.
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) 11194 (2R)-2-Amino-2-(2-methoxy-6-methylphenyl)-1-ethanol C10H15NO2 详情 详情
(II) 11182 2,5-Furandione; Maleic anhydride 108-31-6 C4H2O3 详情 详情
(III) 11196 (Z)-4-[[(1R)-2-Hydroxy-1-(2-methoxy-6-methylphenyl)ethyl]amino]-4-oxo-2-butenoic acid C14H17NO5 详情 详情
(IV) 11197 1-[(1R)-2-Hydroxy-1-(2-methoxy-6-methylphenyl)ethyl]-1H-pyrrole-2,5-dione C14H15NO4 详情 详情
(V) 11198 5-[(1R)-2-Hydroxy-1-(2-methoxy-6-methylphenyl)ethyl]-1-methyl-3a,6a-dihydropyrrolo[3,4-d][1,2,3]triazole-4,6(1H,5H)-dione C15H18N4O4 详情 详情
(VI) 11199 3-[(1R)-2-Hydroxy-1-(2-methoxy-6-methylphenyl)ethyl]-6-methyl-3,6-diazabicyclo[3.1.0]hexane-2,4-dione C15H18N2O4 详情 详情
(VII) 11200 (1R)-4-Acryloyl-10,10-dimethyl-3lambda(6)-thia-4-azatricyclo[5.2.1.0(1,5)]decane-3,3-dione C13H19NO3S 详情 详情
(VIII) 11201 (1R)-4-([(1S,5S,6R)-3-[(1R)-2-Hydroxy-1-(2-methoxy-6-methylphenyl)ethyl]-8-methyl-2,4-dioxo-3,8-diazabicyclo[3.2.1]oct-6-yl]carbonyl)-10,10-dimethyl-3lambda(6)-thia-4-azatricyclo[5.2.1.0(1,5)]decane-3,3-dione C28H37N3O7S 详情 详情
(IX) 11202 (1R)-4-([(1S,5S,6R)-3-[(1R)-2-(Methoxymethoxy)-1-(2-methoxy-6-methylphenyl)ethyl]-8-methyl-2,4-dioxo-3,8-diazabicyclo[3.2.1]oct-6-yl]carbonyl)-10,10-dimethyl-3lambda(6)-thia-4-azatricyclo[5.2.1.0(1,5)]decane-3,3-dione C30H41N3O8S 详情 详情
(X) 11203 (1R)-4-([(1S,5S,6R)-3-[(1R)-1-[2-(Bromomethyl)-6-methoxyphenyl]-2-(methoxymethoxy)ethyl]-8-methyl-2,4-dioxo-3,8-diazabicyclo[3.2.1]oct-6-yl]carbonyl)-10,10-dimethyl-3lambda(6)-thia-4-azatricyclo[5.2.1.0(1,5)]decane-3,3-dione C30H40BrN3O8S 详情 详情
(XI) 11204 [2-[(1R)-1-((1S,5S,6R)-6-[[(1R)-10,10-Dimethyl-3,3-dioxo-3lambda(6)-thia-4-azatricyclo[5.2.1.0(1,5)]dec-4-yl]carbonyl]-8-methyl-2,4-dioxo-3,8-diazabicyclo[3.2.1]oct-3-yl)-2-(methoxymethoxy)ethyl]-3-methoxybenzyl](triphenyl)phosphonium bromide C48H55BrN3O8PS 详情 详情
(XII) 11205 (1R)-4-([(1S,10R,13S,15R)-8-Methoxy-10-[(methoxymethoxy)methyl]-16-methyl-12-oxo-11,16-diazatetracyclo[11.2.1.0(2,11).0(4,9)]hexadeca-2,4,6,8-tetraen-15-yl]carbonyl)-10,10-dimethyl-3lambda(6)-thia-4-azatricyclo[5.2.1.0(1,5)]decane-3,3-dione C30H39N3O7S 详情 详情
(XIII) 11206 (1R)-4-([(1S,2S,10R,13S,15R)-8-Methoxy-10-[(methoxymethoxy)methyl]-16-methyl-12-oxo-11,16-diazatetracyclo[11.2.1.0(2,11).0(4,9)]hexadeca-4,6,8-trien-15-yl]carbonyl)-10,10-dimethyl-3lambda(6)-thia-4-azatricyclo[5.2.1.0(1,5)]decane-3,3-dione C30H41N3O7S 详情 详情
(XIV) 11207 (1S,2S,10R,13S,15R)-8-Methoxy-10-[(methoxymethoxy)methyl]-16-methyl-12-oxo-11,16-diazatetracyclo[11.2.1.0(2,11).0(4,9)]hexadeca-4,6,8-triene-15-carboxylic acid C20H26N2O6 详情 详情
(XV) 11208 (1S,2S,10R,13S,15R)-10-(Hydroxymethyl)-8-methoxy-16-methyl-12-oxo-11,16-diazatetracyclo[11.2.1.0(2,11).0(4,9)]hexadeca-4,6,8-triene-15-carboxylic acid C18H22N2O5 详情 详情
Extended Information