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【结 构 式】 
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【分子编号】42380 【品名】tert-butyl(dimethyl)silyl (1R)-2-(2-ethoxyethoxy)-1-[[(2S)-2-methyloxiranyl]methyl]ethyl ether; (5R)-2,2,3,3-tetramethyl-5-[[(2S)-2-methyloxiranyl]methyl]-4,7,10-trioxa-3-siladodecane 【CA登记号】 |
【 分 子 式 】C16H34O4Si 【 分 子 量 】318.52906 【元素组成】C 60.33% H 10.76% O 20.09% Si 8.82% |
合成路线1
该中间体在本合成路线中的序号：(XIV)Synthesis of intermediate (XIV): The condensation of epoxide (VIII) with isopropenyl bromide (IX) by means of n-BuLi and CuCN gives the alcohol (X), which is treated with 2-(tert-butoxycarbonyloxyimino)-2-phenylacetonitrile (Boc-ON) and n-BuLi in toluene to yield the cyclic carbonate (XI). The epoxidation of (XI) with HOAc in THF affords the epoxide (XII), which is selectively monoprotected with ethyl vinyl ether to provide the secondary alcohol (XIII). Finally this compound is silylated with TBDMSCl and imidazole to furnish the desired intermediate (XIV).
| 【1】 Guo, J.; et al.; Total synthesis of altohyrtin A (spongistatin 1): Part 1. Angew Chem. Int Ed Engl 1998, 37, 1-2, 187. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 18762 | 1-Ethoxyethylene; Ethyl vinyl ether；Ethoxyethene | 109-92-2 | C4H8O | 详情 | 详情 | |
| (VIII) | 42374 | tert-butyl(dimethyl)[(2R)oxiranylmethoxy]silane; tert-butyl(dimethyl)silyl (2R)oxiranylmethyl ether | C9H20O2Si | 详情 | 详情 | |
| (IX) | 42375 | 2-bromo-1-propene；2-bromopropene;Isopropenyl bromide;a-Methylvinyl bromide | 557-93-7 | C3H5Br | 详情 | 详情 |
| (X) | 42376 | (2R)-1-[[tert-butyl(dimethyl)silyl]oxy]-4-methyl-4-penten-2-ol | C12H26O2Si | 详情 | 详情 | |
| (XI) | 42377 | (4S,6R)-6-([[tert-butyl(dimethyl)silyl]oxy]methyl)-4-(iodomethyl)-4-methyl-1,3-dioxan-2-one | C13H25IO4Si | 详情 | 详情 | |
| (XII) | 42378 | (2R)-3-[(2S)-2-methyloxiranyl]-1,2-propanediol | C6H12O3 | 详情 | 详情 | |
| (XIII) | 42379 | (2R)-1-(2-ethoxyethoxy)-3-[(2S)-2-methyloxiranyl]-2-propanol | C10H20O4 | 详情 | 详情 | |
| (XIV) | 42380 | tert-butyl(dimethyl)silyl (1R)-2-(2-ethoxyethoxy)-1-[[(2S)-2-methyloxiranyl]methyl]ethyl ether; (5R)-2,2,3,3-tetramethyl-5-[[(2S)-2-methyloxiranyl]methyl]-4,7,10-trioxa-3-siladodecane | C16H34O4Si | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XIV)Synthesis of intermediate (XLIII): The condensation of dithiane intermediate (VII) with epoxide intermediate (XIV) by means of NaOtBu and n-BuLi gives alcohol (XXXIV), which is converted into epoxide (XXXV) by treatment with pyridinium p-toluenesulfonate (PPTS), NaH and tosyl-imidazole in THF. The condensation of (XXXV) with intermediate iodovinyl compound (XX) by means of n-BuLi in THF yields the diol (XXXVI), which is treated with CaCO3 and NIS to afford the spiroketal (XXXVII). The monoacylation of (XXXVIII) with methoxyacetyl chloride (XXXVIII) and LiNH2, followed by cleavage of the cyclohexylidene ketal with PPTS, provides the triol (XXXIX), which is selectively silylated at the primary OH group with TBDMSCl to give the silyl ether (LX). The acylation of the two secondary OH groups of (LX) with Ac2O and DMAP yields the diacetate (XLI), which is desilylated with HF and pyridine in acetonitrile afford the primary alcohol (XLII). Finally, this compound is oxidized with DMP in dichloromethane to furnish the desired intermediate aldehyde (XLIII).
| 【1】 Guo, J.; et al.; Total synthesis of altohyrtin A (spongistatin 1): Part 1. Angew Chem. Int Ed Engl 1998, 37, 1-2, 187. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (VII) | 42373 | benzyl (3S,5S)-3,5-bis[[tert-butyl(diphenyl)silyl]oxy]-6-(1,3-dithian-2-yl)hexyl ether; (5S,7S)-5-[2-(benzyloxy)ethyl]-7-(1,3-dithian-2-ylmethyl)-2,2,10,10-tetramethyl-3,3,9,9-tetraphenyl-4,8-dioxa-3,9-disilaundecane | C49H62O3S2Si2 | 详情 | 详情 | |
| (XIV) | 42380 | tert-butyl(dimethyl)silyl (1R)-2-(2-ethoxyethoxy)-1-[[(2S)-2-methyloxiranyl]methyl]ethyl ether; (5R)-2,2,3,3-tetramethyl-5-[[(2S)-2-methyloxiranyl]methyl]-4,7,10-trioxa-3-siladodecane | C16H34O4Si | 详情 | 详情 | |
| (XX) | 42386 | (2R,3R)-2-[(1S)-2-iodo-1-methyl-2-propenyl]-3-methyl-1,5-dioxaspiro[5.5]undecane | C14H23IO2 | 详情 | 详情 | |
| (XXXIV) | 42396 | (2S,4R)-1-[2-((2S,4S)-6-(benzyloxy)-2,4-bis[[tert-butyl(diphenyl)silyl]oxy]hexyl)-1,3-dithian-2-yl]-4-[[tert-butyl(dimethyl)silyl]oxy]-5-(2-ethoxyethoxy)-2-methyl-2-pentanol | C65H96O7S2Si3 | 详情 | 详情 | |
| (XXXV) | 42397 | (2S)-1-[2-((2S,4S)-6-(benzyloxy)-2,4-bis[[tert-butyl(diphenyl)silyl]oxy]hexyl)-1,3-dithian-2-yl]-2-methyl-3-[(2R)oxiranyl]-2-propanol | C55H72O5S2Si2 | 详情 | 详情 | |
| (XXXVI) | 42398 | (2S,4S)-1-[2-((2S,4S)-6-(benzyloxy)-2,4-bis[[tert-butyl(diphenyl)silyl]oxy]hexyl)-1,3-dithian-2-yl]-2-methyl-6-[(1R)-1-[(2S,3R)-3-methyl-1,5-dioxaspiro[5.5]undec-2-yl]ethyl]-6-heptene-2,4-diol | C69H96O7S2Si2 | 详情 | 详情 | |
| (XXXVII) | 42399 | (2S,4S,6S,8S,10S)-8-[2-(benzyloxy)ethyl]-4-methyl-2-(2-[(1R)-1-[(2S,3R)-3-methyl-1,5-dioxaspiro[5.5]undec-2-yl]ethyl]-2-propenyl)-1,7-dioxaspiro[5.5]undecane-4,10-diol | C34H52O7 | 详情 | 详情 | |
| (XXXVIII) | 13429 | 2-Methoxyacetyl chloride; Methoxyacetyl chloride | 38870-89-2 | C3H5ClO2 | 详情 | 详情 |
| (XXXIX) | 42400 | 2-((2S,4S,6S,8S,10S)-8-[2-[(1R,2S,3R)-2,4-dihydroxy-1,3-dimethylbutyl]-2-propenyl]-4,10-dihydroxy-10-methyl-1,7-dioxaspiro[5.5]undec-2-yl)ethyl 2-methoxyacetate | C24H42O9 | 详情 | 详情 | |
| (XL) | 42401 | 2-[(2S,4S,8S,10S)-8-[2-((1R,2S,3R)-4-[[tert-butyl(dimethyl)silyl]oxy]-2-hydroxy-1,3-dimethylbutyl)-2-propenyl]-4,10-dihydroxy-10-methyl-1,7-dioxaspiro[5.5]undec-2-yl]ethyl 2-methoxyacetate | C30H56O9Si | 详情 | 详情 | |
| (XLI) | 42402 | 2-[(2S,4S,8S,10S)-4-(acetoxy)-8-[2-((1R,2S,3R)-2-(acetoxy)-4-[[tert-butyl(dimethyl)silyl]oxy]-1,3-dimethylbutyl)-2-propenyl]-10-hydroxy-10-methyl-1,7-dioxaspiro[5.5]undec-2-yl]ethyl 2-methoxyacetate | C34H60O11Si | 详情 | 详情 | |
| (XLII) | 42403 | 2-((2S,4S,6S,8S,10S)-4-(acetoxy)-8-[2-[(1R,2S,3R)-2-(acetoxy)-4-hydroxy-1,3-dimethylbutyl]-2-propenyl]-10-hydroxy-10-methyl-1,7-dioxaspiro[5.5]undec-2-yl)ethyl 2-methoxyacetate | C28H46O11 | 详情 | 详情 | |
| (XLIII) | 42404 | 2-((2S,4S,6S,8S,10S)-4-(acetoxy)-8-[2-[(1R,2S,3S)-2-(acetoxy)-1,3-dimethyl-4-oxobutyl]-2-propenyl]-10-hydroxy-10-methyl-1,7-dioxaspiro[5.5]undec-2-yl)ethyl 2-methoxyacetate | C28H44O11 | 详情 | 详情 |