|
【结 构 式】 
|
【分子编号】55704 【品名】(1R,9S,12S,13S,14S,17R,21S,23S,24R,25S,27R)-12-[(E)-2-((1R,3R,4R)-4-{[(2-bromophenyl)(dimethyl)silyl]oxy}-3-methoxycyclohexyl)-1-methylethenyl]-14-{[tert-butyl(dimethyl)silyl]oxy}-17-ethyl-1-hydroxy-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.0~4,9~]octacos-18-ene-2,3,10,16-tetrone 【CA登记号】 |
【 分 子 式 】C57H92BrNO12Si2 【 分 子 量 】1119.43202 【元素组成】C 61.16% H 8.28% Br 7.14% N 1.25% O 17.15% Si 5.02% |
合成路线1
该中间体在本合成路线中的序号：(V)The reaction of ascomycin (I) with Tbdms-Cl and imidazole gives the bis silylated compound (II), which is regioselectively monodesilylated by means of aq. HF in acetonitrile to yield the monosilylated compound (III). The silylation of (III) with 2-bromophenyldimethylsilyl chloride (IV) and imidazole affords the new disilylated compound (V), which is submitted to radical translocating/reducing conditions by means of Et3N/O2 as radical initiator and Bu3Sn2H as deuterium source. Under these conditions a mixture of labeled compounds (VI) and (VII) is obtained where about 70% is the ascomycin labeled compound (VI) and 30% the aromatic labeled compound (VII).
| 【1】 Acemoglu, M.; et al.; Regio- and stereoselective preparation of ascomycin-d1 and FK 506-d1. J Label Compd Radiopharm 2002, 45, 5, 361. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (VI),(VII) | 55705 | (1R,9S,12S,13S,14S,17R,21S,23S,24R,25S,27R)-14-{[tert-butyl(dimethyl)silyl]oxy}-12-[(E)-2-((1R,3R,4R)-4-{[dimethyl(phenyl)silyl]oxy}-3-methoxycyclohexyl)-1-methylethenyl]-17-ethyl-1-hydroxy-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.0~4,9~]octacos-18-ene-2,3,10,16-tetrone | C57H93NO12Si2 | 详情 | 详情 | |
| (I) | 14951 | (1R,9S,12S,13R,14S,17R,21S,23S,24R,25S,27R)-17-ethyl-1,14-dihydroxy-12-[(E)-2-[(1R,3R,4R)-4-hydroxy-3-methoxycyclohexyl]-1-methylethenyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.0(4,9)]octacos-18-ene-2,3,10,16-tetron | C43H69NO12 | 详情 | 详情 | |
| (II) | 22753 | (1R,9S,12S,13S,14S,17R,21S,23S,24R,25S,27R)-14-[[tert-butyl(dimethyl)silyl]oxy]-12-[(E)-2-((1R,3R,4R)-4-[[tert-butyl(dimethyl)silyl]oxy]-3-methoxycyclohexyl)-1-methylethenyl]-17-ethyl-1-hydroxy-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.0(4,9)]octacos-18-ene-2,3,10,16-tetrone | C55H97NO12Si2 | 详情 | 详情 | |
| (III) | 22754 | (1R,9S,12S,13S,14S,17R,21S,23S,24R,25S,27R)-14-[[tert-butyl(dimethyl)silyl]oxy]-17-ethyl-1-hydroxy-12-[(E)-2-[(1R,3R,4R)-4-hydroxy-3-methoxycyclohexyl]-1-methylethenyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.0(4,9)]octacos-18-ene-2,3,10,16-tetrone | C49H83NO12Si | 详情 | 详情 | |
| (IV) | 55699 | (2-bromophenyl)(chloro)dimethylsilane | C8H10BrClSi | 详情 | 详情 | |
| (V) | 55704 | (1R,9S,12S,13S,14S,17R,21S,23S,24R,25S,27R)-12-[(E)-2-((1R,3R,4R)-4-{[(2-bromophenyl)(dimethyl)silyl]oxy}-3-methoxycyclohexyl)-1-methylethenyl]-14-{[tert-butyl(dimethyl)silyl]oxy}-17-ethyl-1-hydroxy-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.0~4,9~]octacos-18-ene-2,3,10,16-tetrone | C57H92BrNO12Si2 | 详情 | 详情 | |
| (VI) | 55706 | (1R,9S,12S,13S,14S,17R,21S,23S,24R,25S,27R)-14-{[tert-butyl(dimethyl)silyl]oxy}-12-[(E)-2-((1R,3R,4R)-4-{[dimethyl(phenyl)silyl]oxy}-3-methoxycyclohexyl)-1-methylethenyl]-17-ethyl-1-hydroxy-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.0~4,9~]octacos-18-ene-2,3,10,16-tetrone | C57H93NO12Si2 | 详情 | 详情 | |
| (VII) | 55707 | (1R,9S,12S,13S,14S,17R,21S,23S,24R,25S,27R)-14-{[tert-butyl(dimethyl)silyl]oxy}-12-[(E)-2-((1R,3R,4R)-4-{[dimethyl(phenyl)silyl]oxy}-3-methoxycyclohexyl)-1-methylethenyl]-17-ethyl-1-hydroxy-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.0~4,9~]octacos-18-ene-2,3,10,16-tetrone | C57H93NO12Si2 | 详情 | 详情 |