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【结 构 式】

【分子编号】15020

【品名】2-((1R,3R,4R)-4-[[tert-butyl(dimethyl)silyl]oxy]-3-methoxycyclohexyl)-N,N-dimethylacetamide

【CA登记号】

【 分 子 式 】C17H35NO3Si

【 分 子 量 】329.55534

【元素组成】C 61.96% H 10.7% N 4.25% O 14.56% Si 8.52%

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:(XXXII)

The new intermediates, the oxazolidinone (XX) and the aldehyde (XXI), are obtained as follows: Oxazolidinone (XX): The ring opening of cyclohexane epoxide (XXVI) with methanol and CSA followed by silylation with tert-butyldimethylsilyl trifluoromethanesulfonate in dichloromethane gives compound (XXVII), which is debenzylated by hydrogenolysis and oxidized with oxalyl chloride to the cyclohexanone (XXVIII). Dehydrogenation of (XXVIII) by treatment with lithium diiosopropylamide (LDA), tosyl chloride and palladium diacetate yields the cyclohexenone (XXIX), which is reduced with LiBH4 - CeCl3 in methanol/THF to the cyclohexenol (XXX). The condensation of (XXX) with dimethylacetamide diethylacetal (XXXI) in refluxing xylene affords the cyclohexylacetamide (XXXII), which is reduced with lithium triethylborohydride in THF and with H2 over Pd/C in ethanol to give the cyclohexylethanol (XXXIII). The dehydration of (XXXIII) through a selenium derivative yields the vinyl compound (XXXIV), which is oxidized with ozone to the aldehyde (XXXV). Finally, the condensation of (XXXV) with the phosphonate (XXXVI) by means of IEN and LiCl in acetonitrile followed by a desilylation with HF and silylation with tert-butyldiphenylsilyl chloride in DMF yields the oxazolidinone (XX) (see K.C. Nicolau et al., J Chem Soc Chem Commun 1993, 7: 619). (1,2)

1 Nicolaou, K.C.; Piscopio, A.D.; Bertinato, P.; Chakraborty, T.K.; Minowa, N.; Koide, K.; Total Synthesis of Rapamycin. Chemistry (Weinheim) 1995, 1, 5, 318.
2 Nicolaou, K.C.; Chakraborty, T.K.; Piscopio, A.D.; Minowa, N.; Bertinato, P.; Total synthesis of rapamycin. J Am Chem Soc 1993, 115, 10, 4419.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XX) 15008 (4R,5S)-3-[3-((1S,3R)-4-[[tert-butyl(diphenyl)silyl]oxy]-3-methoxycyclohexyl)propanoyl]-4-methyl-5-phenyl-1,3-oxazolidin-2-one C36H45NO5Si 详情 详情
(XXVI) 15014 benzyl (1S,2R,6S)-7-oxabicyclo[4.1.0]hept-2-yl ether; (1S,2R,6S)-2-(benzyloxy)-7-oxabicyclo[4.1.0]heptane C13H16O2 详情 详情
(XXVII) 15015 benzyl (1R,2S,3R)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methoxycyclohexyl ether; [[(1S,2R,6R)-2-(benzyloxy)-6-methoxycyclohexyl]oxy](tert-butyl)dimethylsilane C20H34O3Si 详情 详情
(XXVIII) 15016 (2S,3R)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methoxycyclohexanone C13H26O3Si 详情 详情
(XXIX) 15017 (5R,6S)-6-[[tert-butyl(dimethyl)silyl]oxy]-5-methoxy-2-cyclohexen-1-one C13H24O3Si 详情 详情
(XXX) 15018 (1S,5R,6R)-6-[[tert-butyl(dimethyl)silyl]oxy]-5-methoxy-2-cyclohexen-1-ol C13H26O3Si 详情 详情
(XXXI) 15019 N-(1,1-diethoxyethyl)-N,N-dimethylamine; 1,1-diethoxy-N,N-dimethyl-1-ethanamine C8H19NO2 详情 详情
(XXXII) 15020 2-((1R,3R,4R)-4-[[tert-butyl(dimethyl)silyl]oxy]-3-methoxycyclohexyl)-N,N-dimethylacetamide C17H35NO3Si 详情 详情
(XXXIII) 15021 2-((1S,3R,4R)-4-[[tert-butyl(dimethyl)silyl]oxy]-3-methoxycyclohexyl)-1-ethanol C15H32O3Si 详情 详情
(XXXIV) 15022 tert-butyl(dimethyl)silyl (1R,2R,4R)-2-methoxy-4-vinylcyclohexyl ether; tert-butyl[[(1R,2R,4R)-2-methoxy-4-vinylcyclohexyl]oxy]dimethylsilane C15H30O2Si 详情 详情
(XXXV) 15023 (1R,3R,4R)-4-[[tert-butyl(dimethyl)silyl]oxy]-3-methoxycyclohexanecarbaldehyde C14H28O3Si 详情 详情
(XXXVI) 15024 diethyl 2-[(4R,5S)-4-methyl-2-oxo-5-phenyl-1,3-oxazolan-3-yl]-2-oxoethylphosphonate C16H22NO6P 详情 详情
Extended Information