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【结 构 式】 
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【分子编号】63895 【品名】(1E,3S,4S,6E)-4-[(4-methoxybenzyl)oxy]-1-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-8-(trityloxy)-1,6-octadien-3-ol 【CA登记号】 |
【 分 子 式 】C41H44O5 【 分 子 量 】616.79736 【元素组成】C 79.84% H 7.19% O 12.97% |
合成路线1
该中间体在本合成路线中的序号：(XXXIV)Synthesis of the target Laulimalide. The condensation of the tin derivative (XXVI) with the chiral isopropenyl boron derivative (XXVII) gives the secondary alcohol (XXVIII), which is alkylated with allyl bromide (XXIX) and KHMDS to yield the allyl ether (XXX). The ring closing metathesis reaction in (XXX) by means of Schrock catalyst affords the dihydropyranyl stannane (XXXI), which is treated with N-iodosuccinimide to provide the iodovinyl compound (XXXII). The reaction of (XXXII) with BuLi and MgBr2 gives the vinylmagnesium derivative (XXXIII), which is condensed with the unsaturated aldehyde intermediate (XXV) to yield the olefinic alcohol (XXXIV). The reaction of (XXXIV) with Tbdms-Cl and imidazole affords the silyl ether (XXXV), which is selectively deprotected with formic acid, and oxidated with DMP to provide the chiral unsaturated aldehyde (XXXVI).
| 【1】 Nelson, S.G.; Cheung, W.S.; Kassick, A.J.; Hilfiker, M.A.; A de novo enantioselective total synthesis of (-)-laulimalide. J Am Chem Soc 2002, 124, 46, 13654. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXV) | 63887 | (2S,4E)-2-[(4-methoxybenzyl)oxy]-6-(trityloxy)-4-hexenal | C33H32O4 | 详情 | 详情 | |
| (XXVI) | 63888 | (E)-3-(tributylstannyl)-2-propenal | C15H30OSn | 详情 | 详情 | |
| (XXVII) | 63889 | C5H11B | 详情 | 详情 | ||
| (XXVIII) | 63890 | (1E)-5-methyl-1-(tributylstannyl)-1,5-hexadien-3-ol | C19H38OSn | 详情 | 详情 | |
| (XXIX) | 11463 | 3-Bromo-1-propene; 3-Bromopropene；allyl bromide | 106-95-6 | C3H5Br | 详情 | 详情 |
| (XXX) | 63891 | [(1E)-3-(allyloxy)-5-methyl-1,5-hexadienyl](tributyl)stannane; allyl 3-methyl-1-[(E)-2-(tributylstannyl)ethenyl]-3-butenyl ether | C22H42OSn | 详情 | 详情 | |
| (XXXI) | 63894 | tributyl{(E)-2-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]ethenyl}stannane | C20H38OSn | 详情 | 详情 | |
| (XXXII) | 63893 | (2S)-2-[(E)-2-iodoethenyl]-4-methyl-3,6-dihydro-2H-pyran | C8H11IO | 详情 | 详情 | |
| (XXXIII) | 63892 | bromo{(E)-2-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]ethenyl}magnesium | C8H11BrMgO | 详情 | 详情 | |
| (XXXIV) | 63895 | (1E,3S,4S,6E)-4-[(4-methoxybenzyl)oxy]-1-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-8-(trityloxy)-1,6-octadien-3-ol | C41H44O5 | 详情 | 详情 | |
| (XXXV) | 63896 | tert-butyl(dimethyl)silyl (1S,2S,4E)-2-[(4-methoxybenzyl)oxy]-1-{(E)-2-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]ethenyl}-6-(trityloxy)-4-hexenyl ether; tert-butyl{[(1S,2S,4E)-2-[(4-methoxybenzyl)oxy]-1-{(E)-2-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]ethenyl}-6-(trityloxy)-4-hexenyl]oxy}dimethylsilane | C47H58O5Si | 详情 | 详情 | |
| (XXXVI) | 63897 | (2E,5S,6S,7E)-6-{[tert-butyl(dimethyl)silyl]oxy}-5-[(4-methoxybenzyl)oxy]-8-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-2,7-octadienal | C28H42O5Si | 详情 | 详情 |