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【结 构 式】 
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【分子编号】26406 【品名】 【CA登记号】 |
【 分 子 式 】C93H108Br2Cl2I2O29S2Se 【 分 子 量 】2317.47746 【元素组成】C 48.2% H 4.7% Br 6.9% Cl 3.06% I 10.95% O 20.02% S 2.77% Se 3.41% |
合成路线1
该中间体在本合成路线中的序号：(VIII)The condensation of the protected aglucone (I) with the glucoside (II) by means of TBS triflate gives the condensed alpha-glucoside (III), which is worked up to yield the bis-chloroacetylated intermediate that is desilylated to compound (IV). The condensation of (IV) with disaccharide (V) gives the trisaccharide (VI), which by deprotection of the phenolic chloroacetate and condensation with disaccharide (VII) affords the pentasaccharide (VIII).
| 【1】 Roush, W.R.; et al.; Total synthesis of olivomycin A. J Am Chem Soc 1999, 121, 9, 1990. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 26399 | (3R)-8-[(benzyloxy)methoxy]-6,9-bis[(E)-2-butenyloxy]-2-hydroxy-3-[(1S)-1-methoxy-2-[(2R,3R)-3-methyl-1,4-dioxaspiro[4.4]non-2-yl]-2-oxoethyl]-3,4-dihydro-1(2H)-anthracenone | C41H48O10 | 详情 | 详情 | |
| (II) | 26400 | (2S,3R,4S,5R,6R)-2-(bromomethyl)-5-(phenylsulfanyl)-6-[(2,2,2-trichloroethanimidoyl)oxy]-4-[(triethylsilyl)oxy]tetrahydro-2H-pyran-3-yl 2-chloroacetate | C22H30BrCl4NO5SSi | 详情 | 详情 | |
| (III) | 26401 | 8-(Benzyloxymethoxy)-2-[6-bromo-4-O-(2-chloroacetyl)-2,6-dideoxy-2-(phenylsulfanyl)-3-O-(triethylsilyl)-beta-D-glucopyranosyloxy]-6,9-bis(2(E)-butenyloxy)-3(S)-[1(S)-methoxy-2-[5(R)-methylspiro[1,3-dioxolane-2,1'-cyclopent]-4(S)-yl]-2-oxoethyl]-1,2,3,4-tetrahydroanthracen-1-one; 8-(Benzyloxymethoxy)-2-[6-bromo-4-O-(2-chloroacetyl)-2,6-dideoxy-2-(phenylsulfanyl)-3-O-(triethylsilyl)-beta-D-glucopyranosyloxy]-6,9-bis(2(E)-butenyloxy)-3(S)-[1(S)-methoxy-2-[5(R)-methylspiro[1,3-dioxolane-2,1'-cyclopent]-4(S)-yl]-2-oxoethyl]-1,2,3,4-tetrahydroanthracen-1-one | C61H76BrClO14SSi | 详情 | 详情 | |
| (IV) | 26402 | 8-(Benzyloxymethoxy)-2-[6-bromo-4-O-(2-chloroacetyl)-2,6-dideoxy-2-(phenylsulfanyl)-3-O-(triethylsilyl)-beta-D-glucopyranosyloxy]-6-(2-chloroacetoxy)-9-hydroxy-3(S)-[1(S)-methoxy-2-[5(R)-methylspiro[1,3-dioxolane-2,1'-cyclopent]-4(S)-yl]-2-oxoethyl]-1,2,3,4-tetrahydroanthracen-1-one; 8-(Benzyloxymethoxy)-2-[6-bromo-4-O-(2-chloroacetyl)-2,6-dideoxy-2-(phenylsulfanyl)-3-O-(triethylsilyl)-beta-D-glucopyranosyloxy]-6-(2-chloroacetoxy)-9-hydroxy-3(S)-[1(S)-methoxy-2-[5(R)-methylspiro[1,3-dioxolane-2,1'-cyclopent]-4(S)-yl]-2-oxoethyl]-1,2,3,4-tetrahydroanthracen-1-one | C49H51BrCl2O15S | 详情 | 详情 | |
| (V) | 26403 | (2S,3S,4R,5R,6S)-6-([(2S,3S,4S,5R,6R)-2-(bromomethyl)-3-[(2-chloroacetyl)oxy]-5-(phenylsulfanyl)-6-[(2,2,2-trichloroethanimidoyl)oxy]tetrahydro-2H-pyran-4-yl]oxy)-4-hydroxy-5-iodo-2,4-dimethyltetrahydro-2H-pyran-3-yl 2-methylpropanoate | C27H33BrCl4INO9S | 详情 | 详情 | |
| (VI) | 26404 | C72H81Br2Cl2IO22S2 | 详情 | 详情 | ||
| (VII) | 26405 | (2R,3S,4S,5R,6S)-6-hydroxy-4-[[(2R,3S,4S,5R,6R)-4-hydroxy-3-iodo-5-methoxy-6-methyltetrahydro-2H-pyran-2-yl]oxy]-2-methyl-5-(phenylselanyl)tetrahydro-2H-pyran-3-yl acetate | C21H29IO8Se | 详情 | 详情 | |
| (VIII) | 26406 | C93H108Br2Cl2I2O29S2Se | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(VIII)The elimination of the diol protecting group of compound (VIII) with CSA in methanol followed by silylation with TES triflate affords the silylated pentasaccharide (IX), which is finally desulfurized and deiodinated by hydrogenolysis with Et3B and Bu3SnH, and with RaNi to eliminate also the BOM protecting group, and with FH in pyridine to eliminate the silyl and chloroacetyl groups affording the target olivomycin A.
