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【结 构 式】

【分子编号】35713

【品名】 

【CA登记号】

【 分 子 式 】C36H50O8Si

【 分 子 量 】638.8737

【元素组成】C 67.68% H 7.89% O 20.03% Si 4.4%

与该中间体有关的原料药合成路线共 4 条

合成路线1

该中间体在本合成路线中的序号:(XLI)

The cleavage of the 4-methoxybenzyl group of (XXXIII) with DDQ in dichloromethane/water gives the secondary alcohol (XXXIV), which is oxidized with pyridinium dichromate (PDC) in dichloromethane yielding the corresponding ketone (XXXV). The cyclization of (XXXV) with AcOH affords the tetracyclic compound (XXXVI), which is silylated at the carbinol group with Tes-OTf and lutidine giving the silyl ether (XXXVII). The oxidation of (XXXVII) with DMP in refluxing benzene affords the carbinol (XXXVIII), which is selectively desilylated and cyclized with TFA in dichloromethane/water giving the pentacyclic compound (XXXIX). The oxidation of the hydroxymethyl group of (XXXIX) with DMP in dichloromethane yields corresponding aldehyde (XL), which is silylated at the remaining OH group with Tbdms-OTf and lutidine in dichloromethane to afford the silyl ether (XLI). The oxidation of the aldehyde group of (XLI) with NaClO2 in tert-butanol/water gives the carboxylic acid (XLII).

1 Nicolaou, K.C.; et al.; Total synthesis of the CP molecules CP-225,917 and CP-263,114 - Part 2: Evolution of the final strategy. Angew Chem. Int Ed Engl 1999, 38, 11, 1677.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XXXIII) 35705   C47H68O8Si 详情 详情
(XXXIV) 35706   C39H60O8Si 详情 详情
(XXXV) 35707   C39H58O8Si 详情 详情
(XXXVI) 35708   C36H54O8Si 详情 详情
(XXXVII) 35709   C42H68O8Si2 详情 详情
(XXXVIII) 35710   C42H68O9Si2 详情 详情
(XXXIX) 35711   C30H38O8 详情 详情
(XL) 35712   C30H36O8 详情 详情
(XLI) 35713   C36H50O8Si 详情 详情
(XLII) 35714   C36H50O9Si 详情 详情

合成路线2

该中间体在本合成路线中的序号:(XLV)

The silylation at the remaining OH group of (XLIV) with TBDMS-OTf and lutidine in dichloromethane affords the silyl ether (XLV), which is oxidized at the aldehyde group with NaClO2 in tert-butanol/water giving the carboxylic acid (XLVI). The reaction of (XLVI) with methanesulfonyl chloride and Et3N in THF gives the mixed anhydride (XLVII), which is treated with diazomethane in ethyl ether/THF to yield the diazoketone (XLVIII). The rearrangement of (XLVIII) with Ag2O in DMF/water affords the acetic acid derivative (XLIX), which is condensed with indoline (L) by means of EDC and DMAP in CH2Cl2 to provide the acyl indoline (LI). The desilylation of (LI) with TFA/water in dichloromethane gives the secondary alcohol (LII).

1 Nicolaou, K.C.; et al.; Total synthesis of the CP molecules CP-225,917 and CP-263,114 - Part 2: Evolution of the final strategy. Angew Chem. Int Ed Engl 1999, 38, 11, 1677.
2 Nicolaou, K.C.; et al.; The absolute configuration and asymmetric total synthesis of the CP molecules (CP-263,114 and CP-225,917, Phomoidrides B and A). Angew Chem. Int Ed Engl 2000, 39, 10, 1829.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XLIV) 35712   C30H36O8 详情 详情
(XLV) 35713   C36H50O8Si 详情 详情
(XLVI) 35714   C36H50O9Si 详情 详情
(XLVII) 35715   C39H56O9SSi 详情 详情
(XLVIII) 35716   C37H50N2O8Si 详情 详情
(XLIX) 35717   C37H52O9Si 详情 详情
(L) 19652 indoline 496-15-1 C8H9N 详情 详情
(LI) 35718 (9S,12S,13S,15R,18R)-18-[[tert-butyl(dimethyl)silyl]oxy]-9-[2-(2,3-dihydro-1H-indol-1-yl)-2-oxoethyl]-15-[(E)-4-hexenoyl]-12-[(E)-6-octenyl]-5,16,17-trioxapentacyclo[7.7.2.0(1,10).0(2,13).0(3,7)]octadeca-3(7),10-diene-4,6-dione C45H59NO8Si 详情 详情
(LII) 35719 (9S,12S,13S,15R,18S)-9-[2-(2,3-dihydro-1H-indol-1-yl)-2-oxoethyl]-15-[(E)-4-hexenoyl]-18-hydroxy-12-[(E)-6-octenyl]-5,16,17-trioxapentacyclo[7.7.2.0(1,10).0(2,13).0(3,7)]octadeca-3(7),10-diene-4,6-dione C39H45NO8 详情 详情

合成路线3

该中间体在本合成路线中的序号:(XLI)

The cleavage of the 4-methoxybenzyl group of (XXXIII) with DDQ in dichloromethane/water gives the secondary alcohol (XXXIV), which is oxidized with pyridinium dichromate (PDC) in dichloromethane yielding the corresponding ketone (XXXV). The cyclization of (XXXV) with AcOH affords the tetracyclic compound (XXXVI), which is silylated at the carbinol group with Tes-OTf and lutidine giving the silyl ether (XXXVII). The oxidation of (XXXVII) with DMP in refluxing benzene affords the carbinol (XXXVIII) (1), which is selectively desilylated and cyclized with TFA in dichloromethane/water giving the pentacyclic compound (XXXIX). The oxidation of the hydroxymethyl group of (XXXIX) with DMP in dichloromethane yields corresponding aldehyde (XL), which is silylated at the remaining OH group with Tbdms-OTf and lutidine in dichloromethane to afford the silyl ether (XLI). The oxidation of the aldehyde group of (XLI) with NaClO2 in tert-butanol/water gives the carboxylic acid (XLII).

1 Nicolaou, K.C.; et al.; Total synthesis of the CP molecules CP-225,917 and CP-263,114 - Part 2: Evolution of the final strategy. Angew Chem. Int Ed Engl 1999, 38, 11, 1677.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XXXIII) 35705   C47H68O8Si 详情 详情
(XXXIV) 35706   C39H60O8Si 详情 详情
(XXXV) 35707   C39H58O8Si 详情 详情
(XXXVI) 35708   C36H54O8Si 详情 详情
(XXXVII) 35709   C42H68O8Si2 详情 详情
(XXXVIII) 35710   C42H68O9Si2 详情 详情
(XXXIX) 35711   C30H38O8 详情 详情
(XL) 35712   C30H36O8 详情 详情
(XLI) 35713   C36H50O8Si 详情 详情
(XLII) 35714   C36H50O9Si 详情 详情

合成路线4

该中间体在本合成路线中的序号:(XLV)

The silylation at the remaining OH group of (XLIV) with TBDMS-OTf and lutidine in dichloromethane affords the silyl ether (XLV), which is oxidized at the aldehyde group with NaClO2 in tert-butanol/water giving the carboxylic acid (XLVI). The reaction of (XLVI) with methanesulfonyl chloride and Et3N in THF gives the mixed anhydride (XLVII), which is treated with diazomethane in ethyl ether/THF to yield the diazoketone (XLVIII). The rearrangement of (XLVIII) with Ag2O in DMF/water affords the acetic acid derivative (XLIX), which is condensed with indoline (L) by means of EDC and DMAP in dichloromethane to provide the acyl indoline (LI). The desilylation of (LI) with TFA/water in dichloromethane gives the secondary alcohol (LII).

1 Nicolaou, K.C.; et al.; Total synthesis of the CP molecules CP-225,917 and CP-263,114 - Part 2: Evolution of the final strategy. Angew Chem. Int Ed Engl 1999, 38, 11, 1677.
2 Nicolaou, K.C.; et al.; The absolute configuration and asymmetric total synthesis of the CP molecules (CP-263,114 and CP-225,917, Phomoidrides B and A). Angew Chem. Int Ed Engl 2000, 39, 10, 1829.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XLIV) 35712   C30H36O8 详情 详情
(XLV) 35713   C36H50O8Si 详情 详情
(XLVI) 35714   C36H50O9Si 详情 详情
(XLVII) 35715   C39H56O9SSi 详情 详情
(XLVIII) 35716   C37H50N2O8Si 详情 详情
(XLIX) 35717   C37H52O9Si 详情 详情
(L) 19652 indoline 496-15-1 C8H9N 详情 详情
(LI) 35718 (9S,12S,13S,15R,18R)-18-[[tert-butyl(dimethyl)silyl]oxy]-9-[2-(2,3-dihydro-1H-indol-1-yl)-2-oxoethyl]-15-[(E)-4-hexenoyl]-12-[(E)-6-octenyl]-5,16,17-trioxapentacyclo[7.7.2.0(1,10).0(2,13).0(3,7)]octadeca-3(7),10-diene-4,6-dione C45H59NO8Si 详情 详情
(LII) 35719 (9S,12S,13S,15R,18S)-9-[2-(2,3-dihydro-1H-indol-1-yl)-2-oxoethyl]-15-[(E)-4-hexenoyl]-18-hydroxy-12-[(E)-6-octenyl]-5,16,17-trioxapentacyclo[7.7.2.0(1,10).0(2,13).0(3,7)]octadeca-3(7),10-diene-4,6-dione C39H45NO8 详情 详情
Extended Information