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【结 构 式】

【分子编号】58638

【品名】2,2,2-trichloroethyl (1R,2R,3S,13R,15R,16S)-13-[(acetyloxy)methyl]-22-(allyloxy)-15-cyano-3,5-dihydroxy-21-methoxy-6,20-dimethyl-8,10-dioxa-14,24-diazahexacyclo[14.7.1.0~2,14~.0~4,12~.0~7,11~.0~18,23~]tetracosa-4,6,11,18,20,22-hexaene-24-carboxylate

【CA登记号】

【 分 子 式 】C33H34Cl3N3O10

【 分 子 量 】739.00528

【元素组成】C 53.63% H 4.64% Cl 14.39% N 5.69% O 21.65%

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:(XLI)

The selective protection of the phenolic OH of (XXXIII) by means of benzyl bromide and K2CO3 in refluxing acetonitrile gives the benzyl ether (XXXIV), which is reductocyclized by means of Red-Al in THF to yield the oxazolidine (XXXV). The cleavage of the oxazolidine ring of (XXXV) by means of Tms-CN and BF3/Et2O in dichloromethane affords the hydroxy nitrile (XXXVI), which is treated with Ac2O and pyridine to provide the acetate (XXXVII). The desilylation of (XXXVII) with HF in acetonitrile, followed by oxidation with DMP gives the carbaldehyde (XXXVIII), which is submitted to hydrogenolysis of the benzyl ethers by means of H2 over Pd/C in THF, performing a simultaneous cyclization to yield the pentacyclic compound (XXXIX). The reaction of (XXXIX) with allyl bromide (XL) and DIEA affords the allyl ether (XLI), which is treated with K2CO3 in methanol to provide the carbinol (XLII). The reaction of (XLII) with L-cysteine derivative (XLIII) by means of WSCD and DMAP in dichloromethane gives the corresponding ester (XLIV).

1 Abe, M.; Yanagisawa, A.; Tohma, S.; Kan, T.; Fukuyama, T.; Endo, A.; Total synthesis of ecteinascidin 743. J Am Chem Soc 2002, 124, 23, 6552.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XXIX) 58637 2,2,2-trichloroethyl (1R,2R,3S,13R,15R,16S)-13-[(acetyloxy)methyl]-15-cyano-3,5,22-trihydroxy-21-methoxy-6,20-dimethyl-8,10-dioxa-14,24-diazahexacyclo[14.7.1.0~2,14~.0~4,12~.0~7,11~.0~18,23~]tetracosa-4,6,11,18,20,22-hexaene-24-carboxylate C30H30Cl3N3O10 详情 详情
(XXXIII) 58631 2,2,2-trichloroethyl (1R,9S,12R)-3-(benzyloxy)-12-({[tert-butyl(dimethyl)silyl]oxy}methyl)-11-[(1R)-2-hydroxy-1-(6-hydroxy-7-methyl-1,3-benzodioxol-4-yl)ethyl]-4-methoxy-5-methyl-10-oxo-11,13-diazatricyclo[7.3.1.0~2,7~]trideca-2,4,6-triene-13-carbox C40H49Cl3N2O10Si 详情 详情
(XXXIV) 58632 2,2,2-trichloroethyl (1R,9S,12R)-3-(benzyloxy)-11-{(1R)-1-[6-(benzyloxy)-7-methyl-1,3-benzodioxol-4-yl]-2-hydroxyethyl}-12-({[tert-butyl(dimethyl)silyl]oxy}methyl)-4-methoxy-5-methyl-10-oxo-11,13-diazatricyclo[7.3.1.0~2,7~]trideca-2,4,6-triene-13-ca C47H55Cl3N2O10Si 详情 详情
(XXXV) 58633 2,2,2-trichloroethyl (1R,9S,10S,13R,15R)-3-(benzyloxy)-13-[6-(benzyloxy)-7-methyl-1,3-benzodioxol-4-yl]-15-({[tert-butyl(dimethyl)silyl]oxy}methyl)-4-methoxy-5-methyl-11-oxa-14,16-diazatetracyclo[7.6.1.0~2,7~.0~10,14~]hexadeca-2,4,6-triene-16-carbox C47H55Cl3N2O9Si 详情 详情
(XXXVI) 58634 2,2,2-trichloroethyl (1R,9S,10R,12R)-3-(benzyloxy)-11-{(1R)-1-[6-(benzyloxy)-7-methyl-1,3-benzodioxol-4-yl]-2-hydroxyethyl}-12-({[tert-butyl(dimethyl)silyl]oxy}methyl)-10-cyano-4-methoxy-5-methyl-11,13-diazatricyclo[7.3.1.0~2,7~]trideca-2,4,6-triene C48H56Cl3N3O9Si 详情 详情
(XXXVII) 58635 2,2,2-trichloroethyl (1R,9S,10R,12R)-11-{(1R)-2-(acetyloxy)-1-[6-(benzyloxy)-7-methyl-1,3-benzodioxol-4-yl]ethyl}-3-(benzyloxy)-12-({[tert-butyl(dimethyl)silyl]oxy}methyl)-10-cyano-4-methoxy-5-methyl-11,13-diazatricyclo[7.3.1.0~2,7~]trideca-2,4,6-tr C50H58Cl3N3O10Si 详情 详情
(XXXVIII) 58636 2,2,2-trichloroethyl (1R,9S,10R,12R)-11-{(1R)-2-(acetyloxy)-1-[6-(benzyloxy)-7-methyl-1,3-benzodioxol-4-yl]ethyl}-3-(benzyloxy)-10-cyano-12-formyl-4-methoxy-5-methyl-11,13-diazatricyclo[7.3.1.0~2,7~]trideca-2,4,6-triene-13-carboxylate C44H42Cl3N3O10 详情 详情
(XL) 11463 3-Bromo-1-propene; 3-Bromopropene;allyl bromide 106-95-6 C3H5Br 详情 详情
(XLI) 58638 2,2,2-trichloroethyl (1R,2R,3S,13R,15R,16S)-13-[(acetyloxy)methyl]-22-(allyloxy)-15-cyano-3,5-dihydroxy-21-methoxy-6,20-dimethyl-8,10-dioxa-14,24-diazahexacyclo[14.7.1.0~2,14~.0~4,12~.0~7,11~.0~18,23~]tetracosa-4,6,11,18,20,22-hexaene-24-carboxylate C33H34Cl3N3O10 详情 详情
(XLII) 58639 2,2,2-trichloroethyl (1R,2R,3S,13R,15R,16S)-22-(allyloxy)-15-cyano-3,5-dihydroxy-13-(hydroxymethyl)-21-methoxy-6,20-dimethyl-8,10-dioxa-14,24-diazahexacyclo[14.7.1.0~2,14~.0~4,12~.0~7,11~.0~18,23~]tetracosa-4,6,11,18,20,22-hexaene-24-carboxylate C31H32Cl3N3O9 详情 详情
(XLIII) 58640 (2R)-3-(acetylsulfanyl)-2-{[(allyloxy)carbonyl]amino}propanoic acid C9H13NO5S 详情 详情
(XLIV) 58641 2,2,2-trichloroethyl (1R,2R,3S,13R,15R,16S)-13-{[((2R)-3-(acetylsulfanyl)-2-{[(allyloxy)carbonyl]amino}propanoyl)oxy]methyl}-22-(allyloxy)-15-cyano-3,5-dihydroxy-21-methoxy-6,20-dimethyl-8,10-dioxa-14,24-diazahexacyclo[14.7.1.0~2,14~.0~4,12~.0~7,11~ C40H43Cl3N4O13S 详情 详情
Extended Information