【结 构 式】 |
【分子编号】55496 【品名】tert-butyl(diphenyl)silyl (2E,4Z)-5-(trimethylstannyl)-2,4-pentadienyl ether; tert-butyl(diphenyl){[(2E,4Z)-5-(trimethylstannyl)-2,4-pentadienyl]oxy}silane 【CA登记号】 |
【 分 子 式 】C24H34OSiSn 【 分 子 量 】485.32886 【元素组成】C 59.4% H 7.06% O 3.3% Si 5.79% Sn 24.46% |
合成路线1
该中间体在本合成路线中的序号:(XXI)The selective deprotection of the Pmb- group of (XVIII) with DDQ in dichloromethane gives the secondary alcohol (XIX), which is submitted to a highly selective diimide reduction of its ethynylene group by means of 2-nitrobenzenesulfonyl hydrazide (NBSH) in THF/iPr-OH to yield the cis-iodovinyl compound (XX). The condensation of the iodovinyl compound (XX) with tributylstannane (XXI) by means of PdCl2(acetonitrile)2 in DMF affords the adduct (XXII), which is treated with PCl3/pyridine and then oxidized with tBu-OOH and Pmb-OH to provide the phosphate ester (XXIII). Finally, this compound is deprotected with HF/pyridine in acetonitrile to give the target fostriecin.
【1】 Jacobsen, E.N.; Chavez, D.E.; Total synthesis of fostriecin (CI-920). Angew Chem. Int Ed 2001, 40, 19, 3667. |
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) | 55492 | (6R)-6-{(E,3R,4R,6R)-6-{[tert-butyl(dimethyl)silyl]oxy}-8-iodo-4-[(4-methoxybenzyl)oxy]-3-methyl-3-[(triethylsilyl)oxy]-1-octen-7-ynyl}-5,6-dihydro-2H-pyran-2-one | C34H53IO6Si2 | 详情 | 详情 | |
(XIX) | 55494 | (6R)-6-{(E,3R,4R,6R)-6-{[tert-butyl(dimethyl)silyl]oxy}-4-hydroxy-8-iodo-3-methyl-3-[(triethylsilyl)oxy]-1-octen-7-ynyl}-5,6-dihydro-2H-pyran-2-one | C26H45IO5Si2 | 详情 | 详情 | |
(XX) | 55495 | (6R)-6-{(1E,3R,4R,6R,7Z)-6-{[tert-butyl(dimethyl)silyl]oxy}-4-hydroxy-8-iodo-3-methyl-3-[(triethylsilyl)oxy]-1,7-octadienyl}-5,6-dihydro-2H-pyran-2-one | C26H47IO5Si2 | 详情 | 详情 | |
(XXI) | 55496 | tert-butyl(diphenyl)silyl (2E,4Z)-5-(trimethylstannyl)-2,4-pentadienyl ether; tert-butyl(diphenyl){[(2E,4Z)-5-(trimethylstannyl)-2,4-pentadienyl]oxy}silane | C24H34OSiSn | 详情 | 详情 | |
(XXII) | 55497 | (6R)-6-{(1E,3R,4R,6R,7Z,9Z,11E)-6-{[tert-butyl(dimethyl)silyl]oxy}-13-{[tert-butyl(diphenyl)silyl]oxy}-4-hydroxy-3-methyl-3-[(triethylsilyl)oxy]-1,7,9,11-tridecatetraenyl}-5,6-dihydro-2H-pyran-2-one | C47H72O6Si3 | 详情 | 详情 | |
(XXIII) | 55498 | (1R,3R,4Z,6Z,8E)-3-{[tert-butyl(dimethyl)silyl]oxy}-10-{[tert-butyl(diphenyl)silyl]oxy}-1-{(1R,2E)-1-methyl-3-[(2R)-6-oxo-3,6-dihydro-2H-pyran-2-yl]-1-[(triethylsilyl)oxy]-2-propenyl}-4,6,8-decatrienyl bis(4-methoxybenzyl) phosphate | C63H89O11PSi3 | 详情 | 详情 |