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【结 构 式】

【分子编号】41528

【品名】1-benzyl 4-(4-methoxybenzyl) (2S)-2-hydroxybutanedioate

【CA登记号】

【 分 子 式 】C19H20O6

【 分 子 量 】344.3642

【元素组成】C 66.27% H 5.85% O 27.88%

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:(III)

The selective monobenzylation of the hydroxysuccinic acid (I) with trifluoroacetic anhydride and benzyl alcohol gives the monoester (II), which is esterified again with 4-methoxybenzyl chloride (PMB-Cl) and K2CO3 in hot DMF yielding the asymetric diester (III). The reaction of (III) with trifluoromethanesulfonic anhydride, CH3SNa and 15-crown-5 affords the methylsulfanyl derivative (IV), which is selectively debenzylated to give the hemiester (V). The condensation of (V) with the intermediate aminomethyl amide (VI) by means of EDAC and HOBT yields the expected amide (VII), which is oxidized with MCPBA or Oxone to afford the methylsulfanyl derivative (VIIIa-b). Unfortunately, during the preceding oxidation, during a variety of conditions, inevitably lead to epimerization of the stereocenter bearing the methylsulfonyl group. Finally (VIIIa-b) is deprotected by hydrogenolysis with Pd/C and formic acid in methanol. The intermediate aminomethyl amide (VI) has been obtained by condensation of N-benzyloxycarbonyl-L-alanine (X) with glycinamide (IX) by means of CDI and TEA in THF to give the dipeptide (XI), which is submitted to an acidic Hofmann rearrangement using I,I-bis(trifluoroacetoxy)iodobenzene (PIFA) yielding the desired aminomethyl amide (VI).

1 Sutton, A.E.; Clardy, J.; The total synthesis of pantocin B. Org Lett 2000, 2, 3, 319.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(VIIIa) 41533 benzyl (5S,12S)-5-methyl-12-(methylsulfonyl)-3,6,10-trioxo-1-phenyl-2-oxa-4,7,9-triazatridecan-13-oate C24H29N3O8S 详情 详情
(VIIIb) 41534 benzyl (5S,12R)-5-methyl-12-(methylsulfonyl)-3,6,10-trioxo-1-phenyl-2-oxa-4,7,9-triazatridecan-13-oate C24H29N3O8S 详情 详情
(I) 11058 (S)-(+)-Hydroxysuccinic acid; (S)-(+)-Malic acid; (S)-(+)-2-Hydroxybutanedioic acid; L-(-)-Apple acid 97-67-6 C4H6O5 详情 详情
(II) 41527 (3S)-4-(benzyloxy)-3-hydroxy-4-oxobutyric acid C11H12O5 详情 详情
(III) 41528 1-benzyl 4-(4-methoxybenzyl) (2S)-2-hydroxybutanedioate C19H20O6 详情 详情
(IV) 41529 1-benzyl 4-(4-methoxybenzyl) (2R)-2-(methylsulfanyl)butanedioate C20H22O5S 详情 详情
(V) 41530 (3R)-4-(benzyloxy)-3-(methylsulfanyl)-4-oxobutyric acid C12H14O4S 详情 详情
(VI) 41531 benzyl (1S)-2-[(aminomethyl)amino]-1-methyl-2-oxoethylcarbamate C12H17N3O3 详情 详情
(VII) 41532 benzyl (5S,12R)-5-methyl-12-(methylsulfanyl)-3,6,10-trioxo-1-phenyl-2-oxa-4,7,9-triazatridecan-13-oate C24H29N3O6S 详情 详情
(IX) 61209 CBZ-L-Alanine; (2S)-2-[[(Benzyloxy)carbonyl]amino]propionic acid; N-((Phenylmethoxy)carbonyl)-alanine; Carbobenzyloxy-L-alanine C11H13NO4 详情 详情
(X) 41435 N'-[3-(tert-butyl)-5-methoxy-2-(methoxymethoxy)phenyl]-N-(3-pyridinyl)-N-(4-pyridinylmethyl)urea C25H30N4O4 详情 详情
(XI) 41356 tert-butyl (4R)-4-[[(benzyloxy)carbonyl]amino]-4-cyanobutanoate C17H22N2O4 详情 详情
Extended Information