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【结 构 式】 
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【分子编号】11520 【品名】(2R,4S,5R,6S,8R)-8-(1,3-dithian-2-yl)-5-hydroxy-4,6-dimethoxy-2-methylnonyl pivalate 【CA登记号】 |
【 分 子 式 】C21H40O5S2 【 分 子 量 】436.6776 【元素组成】C 57.76% H 9.23% O 18.32% S 14.69% |
合成路线1
该中间体在本合成路线中的序号：(XXI)Selective deprotection of (XVIII) with trifluoroacetic acid in THF - water affords the primary alcohol (XIX), which is oxidized with oxalyl chloride and DMSO in dichloromethane to the aldehyde (XX). The protection of the aldehyde group of (XX) with propane-1,3-dithiol and BF3 gives the dithiane derivative (XXI), which is resilylated with TBS-SO3CF3 as before to the dithiane (XXII). The pivaloyl group of (XXII) is eliminated with LiAlH4 in THF yielding the alcohol (XXIII), which is finally treated with benzenesulfonyl chloride and then with ethyl diphenylphosphine oxide and butyllithium in THF to obtain the first building group, the phosphine derivative (XXIV).
| 【1】 Jones, T.K.; Askin, D.; Mills, S.G.; Reamer, R.A.; Desmond, R.; Volante, R.P.; Tschaen, D.M.; Shinkai, I. (Merck & Co., Inc.); Process for synthesis of FK-506 and tricarbonyl intermediates. EP 0378318; JP 1990233643 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XVIII) | 11517 | (2R,4S,5R,6S,8R)-5,9-bis[[tert-butyl(dimethyl)silyl]oxy]-4,6-dimethoxy-2,8-dimethylnonyl pivalate | C30H64O6Si2 | 详情 | 详情 | |
| (XIX) | 11518 | (2R,4S,5S,6S,8R)-5-[[tert-butyl(dimethyl)silyl]oxy]-9-hydroxy-4,6-dimethoxy-2,8-dimethylnonyl pivalate | C24H50O6Si | 详情 | 详情 | |
| (XX) | 11519 | (2R,4S,5R,6S,8R)-5-[[tert-butyl(dimethyl)silyl]oxy]-4,6-dimethoxy-2,8-dimethyl-9-oxononyl pivalate | C24H48O6Si | 详情 | 详情 | |
| (XXI) | 11520 | (2R,4S,5R,6S,8R)-8-(1,3-dithian-2-yl)-5-hydroxy-4,6-dimethoxy-2-methylnonyl pivalate | C21H40O5S2 | 详情 | 详情 | |
| (XXII) | 11521 | (2R,4S,5R,6S,8R)-5-[[tert-butyl(dimethyl)silyl]oxy]-8-(1,3-dithian-2-yl)-4,6-dimethoxy-2-methylnonyl pivalate | C27H54O5S2Si | 详情 | 详情 | |
| (XXIII) | 11522 | (2R,4S,5R,6S,8R)-5-[[tert-Butyl(dimethyl)silyl]oxy]-8-(1,3-dithian-2-yl)-4,6-dimethoxy-2-methyl-1-nonanol | C22H46O4S2Si | 详情 | 详情 | |
| (XXIV) | 11523 | (3R,5S,6R,7S,9R)-6-[[tert-Butyl(dimethyl)silyl]oxy]-9-(1,3-dithian-2-yl)-5,7-dimethoxy-1,3-dimethyldecyl(diphenyl)phosphine oxide; [(3R,5S,6R,7S,9R)-6-[[tert-Butyl(dimethyl)silyl]oxy]-9-(1,3-dithian-2-yl)-5,7-dimethoxy-1,3-dimethyldecyl](oxo)diphenylphosphorane | C36H59O4PS2Si | 详情 | 详情 |