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【结 构 式】 
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【分子编号】17383 【品名】(10S,12S,13R,14S,16R,28S,31S,32R)-13-[[tert-butyl(dimethyl)silyl]oxy]-31-[(E)-2-((1R,3R,4R)-4-[[tert-butyl(diphenyl)silyl]oxy]-3-methoxycyclohexyl)-1-methylethenyl]-4-hydroxy-12,14-dimethoxy-8,10,16,19,19,32,35,35-octamethyl-2,18,20,30,34,36-hexaoxa-23-azapentacyclo[31.3.1.0(1,6).0(17,21).0(23,28)]heptatriaconta-7,17(21)-diene-22,29-dione 【CA登记号】 |
【 分 子 式 】C72H113NO14Si2 【 分 子 量 】1272.85856 【元素组成】C 67.94% H 8.95% N 1.1% O 17.6% Si 4.41% |
合成路线1
该中间体在本合成路线中的序号：(XV)Ester (XIII) was submitted to cyclization by means of triethylsilyl triflate and 2-chloro-1-methylpyridinium iodide (MCPI) in dichloromethane/methanol gaving the macrocyclic compound (XIV). Elimination of the p-methoxybenzyl group of (XIV) with dichlorodicyanobenzoquinone (DDQ) in dichloromethane yielded the alcohol (XV), which was converted into the iodo derivative (XVI) with I2, triphenylphosphine and imidazole in hot toluene. The reductive fragmentation of the spiroketal rings of (XVI) with zinc/silver-graphite in THF afforded compound (XVII) with the adequate configuration in the C21-C24 fragment.
| 【1】 Liu, L.B.; Roper, T.D.; Gleason, J.L.; Ireland, R.E.; Total synthesis of FK-506. 2. Completion of the synthesis. Tetrahedron 1997, 53, 39, 13257. |
| 【2】 Liu, L.B.; Roper, T.D.; Ireland, R.E.; Total synthesis of FK-506. 1. Construction of the C16-C34 fragment. Tetrahedron 1997, 53, 39, 13221. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIII) | 17381 | 5-((1R,3S,4R,5S,7S,9E)-4-[[tert-butyl(dimethyl)silyl]oxy]-10-[4-((1R,2S,3E)-4-((1R,3R,4R)-4-[[tert-butyl(diphenyl)silyl]oxy]-3-methoxycyclohexyl)-1,3-dimethyl-2-[[(2S)piperidinylcarbonyl]oxy]-3-butenyl)-9-[(4-methoxybenzyl)oxy]-2,2-dimethyl-1,3,7-trioxaspiro[5.5]undec-11-yl]-3,5-dimethoxy-1,7,9-trimethyl-9-decenyl)-2,2-dimethyl-1,3-dioxole-4-carboxylic acid | C80H123NO16Si2 | 详情 | 详情 | |
| (XIV) | 17382 | (10S,12S,13R,14S,16R,28S,31S,32R)-13-[[tert-butyl(dimethyl)silyl]oxy]-31-[(E)-2-((1R,3R,4R)-4-[[tert-butyl(diphenyl)silyl]oxy]-3-methoxycyclohexyl)-1-methylethenyl]-12,14-dimethoxy-4-[(4-methoxybenzyl)oxy]-8,10,16,19,19,32,35,35-octamethyl-2,18,20,30,34,36-hexaoxa-23-azapentacyclo[31.3.1.0(1,6).0(17,21).0(23,28)]heptatriaconta-7,17(21)-diene-22,29-dione | C80H121NO15Si2 | 详情 | 详情 | |
| (XV) | 17383 | (10S,12S,13R,14S,16R,28S,31S,32R)-13-[[tert-butyl(dimethyl)silyl]oxy]-31-[(E)-2-((1R,3R,4R)-4-[[tert-butyl(diphenyl)silyl]oxy]-3-methoxycyclohexyl)-1-methylethenyl]-4-hydroxy-12,14-dimethoxy-8,10,16,19,19,32,35,35-octamethyl-2,18,20,30,34,36-hexaoxa-23-azapentacyclo[31.3.1.0(1,6).0(17,21).0(23,28)]heptatriaconta-7,17(21)-diene-22,29-dione | C72H113NO14Si2 | 详情 | 详情 | |
| (XVI) | 17384 | (10S,12S,13R,14S,16R,28S,31S,32R)-13-[[tert-butyl(dimethyl)silyl]oxy]-31-[(E)-2-((1R,3R,4R)-4-[[tert-butyl(diphenyl)silyl]oxy]-3-methoxycyclohexyl)-1-methylethenyl]-4-iodo-12,14-dimethoxy-8,10,16,19,19,32,35,35-octamethyl-2,18,20,30,34,36-hexaoxa-23-azapentacyclo[31.3.1.0(1,6).0(17,21).0(23,28)]heptatriaconta-7,17(21)-diene-22,29-dione | C72H112INO13Si2 | 详情 | 详情 | |
| (XVII) | 17385 | (9aS,12S,13R,14S,17R,21S,23S,24R,25S,27R)-17-allyl-24-[[tert-butyl(dimethyl)silyl]oxy]-12-[(E)-2-((1R,3R,4R)-4-[[tert-butyl(diphenyl)silyl]oxy]-3-methoxycyclohexyl)-1-methylethenyl]-14-hydroxy-23,25-dimethoxy-2,2,13,19,21,27-hexamethyl-7,8,9,9a,12,13,14,15,20,21,22,23,24,25,26,27-hexadecahydro-4H-[1,3]dioxolo[4,5-f]pyrido[2,1-c][1,4]oxazacyclotricosine-4,10,16(6H,17H)-trione | C69H107NO12Si2 | 详情 | 详情 |