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【结 构 式】

【分子编号】11590

【品名】N-(tert-Butyl)-N-[(E)-2-(triethylsilyl)propylidene]amine; 2-Methyl-N-[(E)-2-(triethylsilyl)propylidene]-2-propanamine

【CA登记号】

【 分 子 式 】C13H29NSi

【 分 子 量 】227.4655

【元素组成】C 68.64% H 12.85% N 6.16% Si 12.35%

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:(XXIII)

The starting compounds (I) and (II) are obtained as follows: Aldehyde (I): The esterification of (R,R)-dihydrobenzoin (IX) with acryloyl chloride (X) by means of triethylamine in dichloromethane gives the corresponding diester (XI), which by bis-cyclization with butadiene (XII) by means of TiCl4 in dichloromethane yields the bis(3-cyclohexenecarboxylic acid) ester (XIII). The hydrolysis of (XIII) with LiOH in methanol affords (R)-3-cyclohexenecarboxylic acid (XIV), which by reaction with I2, KI and NaHCO3 is converted to the iodolactone (XV). The reaction of (XV) with 1,5-diazabicyclo[5.4.0]-5-undecene (DBU) in refluxing THF affords the unsaturated lactone (XVI), which by treatment with NaHCO3 in anhydrous methanol yields (1R,3R)-3-hydroxy-4-cyclohexenecarboxylic acid methyl ester (XVII). The methylation of (XVII) with methyl trifluoromethanesulfonate and 2,6-di-tert-butyl-4-methylpyridine (DBMP) in dichloromethane gives the 3-methoxy ester (XVIII), which is selectively hydroxylated with BH3, H2O2 and NaOH to (1R,3R,4R)-4-hydroxy-3-methoxycyclohexanecarboxylic acid methyl ester (XIX). The protection of (XIX) with triisopropylsilyl (TIPS) trifluoromethanesulfonate (XX) and triethylamine in dichloromethane affords the protected ester (XXI), which is reduced with dibutylaluminum hydride (DIBAL) in hexane to the corresponding aldehyde (XXII). Finally, this compound is condensed with the N-tert-butylimine of 2-(triethylsilyl)propanol (XXIII) by means of butyllithium in THF to afford the desired aldehyde (I).

1 Marshall, J.A.; Xie, S.P.; Synthesis of a C22-34 subunit of the immunosuppressant FK-506. J Org Chem 1995, 60, 22, 7230.
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) 11534 (E)-3-[(1R,3R,4R)-3-Methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-2-methyl-2-propenal C20H38O3Si 详情 详情
(IX) 11576 (1S,2S)-1,2-Diphenyl-1,2-ethanediol; (S,S)-(-)-1,2-Diphenyl-1,2-ethanediol 2325-10-2 C14H14O2 详情 详情
(X) 11577 Acryloyl chloride; Acrylyl chloride;2-Propenoyl chloride 814-68-6 C3H3ClO 详情 详情
(XI) 11578 (1R,2R)-2-(Acryloyloxy)-1,2-diphenylethyl acrylate C20H18O4 详情 详情
(XII) 11579 1,3-Butadiene; Butadiene 106-99-0 C4H6 详情 详情
(XIII) 11580 (1R,2R)-2-[[(1R)-3-cyclohexen-1-ylcarbonyl]oxy]-1,2-diphenylethyl (1R)-3-cyclohexene-1-carboxylate C28H30O4 详情 详情
(XIV) 11581 (1R)-3-Cyclohexene-1-carboxylic acid C7H10O2 详情 详情
(XV) 11582 (1R,4R,5R)-4-Iodo-6-oxabicyclo[3.2.1]octan-7-one C7H9IO2 详情 详情
(XVI) 11583 (1R,5R)-6-Oxabicyclo[3.2.1]oct-3-en-7-one C7H8O2 详情 详情
(XVII) 11584 methyl (1R,5R)-5-hydroxy-3-cyclohexene-1-carboxylate C8H12O3 详情 详情
(XVIII) 11585 methyl (1R,5R)-5-methoxy-3-cyclohexene-1-carboxylate C9H14O3 详情 详情
(XIX) 11586 methyl (1R,3R,4R)-4-hydroxy-3-methoxycyclohexanecarboxylate C9H16O4 详情 详情
(XX) 11587 triisopropylsilyl trifluoromethanesulfonate 80522-42-5 C10H21F3O3SSi 详情 详情
(XXI) 11588 methyl (1R,3R,4R)-3-methoxy-4-[(triisopropylsilyl)oxy]cyclohexanecarboxylate C18H36O4Si 详情 详情
(XXII) 11532 (1R,3R,4R)-3-Methoxy-4-[(triisopropylsilyl)oxy]cyclohexanecarbaldehyde C17H34O3Si 详情 详情
(XXIII) 11590 N-(tert-Butyl)-N-[(E)-2-(triethylsilyl)propylidene]amine; 2-Methyl-N-[(E)-2-(triethylsilyl)propylidene]-2-propanamine C13H29NSi 详情 详情
Extended Information