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【结 构 式】 
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【分子编号】53341 【品名】methyl (2S)-2-{[(benzyloxy)carbonyl]amino}-3-[4-(benzyloxy)-3-iodophenyl]propanoate 【CA登记号】n/a |
【 分 子 式 】C25H24INO5 【 分 子 量 】545.37377 【元素组成】C 55.06% H 4.44% I 23.27% N 2.57% O 14.67% |
合成路线1
该中间体在本合成路线中的序号：(V)The borinated tyrosine intermediate (VII) has been obtained as follows: The esterification of L-tyrosine (I) with SOCl2 and methanol gives the methyl ester (II), which is N-protected with Cbz-Cl and K2CO3 to yield the carbamate (III). The O-protection of (III) with benzyl bromide and Cs2CO3 affords the benzyl ether (IV), which is iodinated with I2 and Ag2SO4 to provide the 3-iodotyrosine derivative (V). Finally, the borylation of (V) by means of pinacolatodiborane (VI) catalyzed by PdCl2[bis(diphenylphosphanyl)ferrocene] (PdCl2(dppf)) gives rise to the target tyrosine intermediate (VII).
| 【1】 Lin, S.N.; Danishefsky, S.J.; The total synthesis of proteasome inhibitors TMC-95A and TMC-95B: Discovery of a new method to generate cis-propenyl amides. Angew Chem. Int Ed 2002, 41, 3, 512. |
| 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) | 48794 | (S)-(-)-Tyrosine; (S)-2-Amino-3-(4-hydroxyphenyl)propionic acid; 3-(4-Hydroxyphenyl)-L-alanine; L-(-)-Tyrosine; L-3-(4-Hydroxyphenyl)alanine; L-4-Hydroxy-17O-phenylalanine; L-beta-(p-Hydroxyphenyl)alanine; L-Hydroxy Phenyl Alanine; L-tyrosine | 60-18-4 | C9H11NO3 | 详情 | 详情 |
| (II) | 21431 | methyl (2S)-2-amino-3-(4-hydroxyphenyl)propanoate | 1080-06-4 | C10H13NO3 | 详情 | 详情 |
| (III) | 53339 | methyl (2S)-2-{[(benzyloxy)carbonyl]amino}-3-(4-hydroxyphenyl)propanoate | n/a | C18H19NO5 | 详情 | 详情 |
| (IV) | 53340 | methyl (2S)-2-{[(benzyloxy)carbonyl]amino}-3-[4-(benzyloxy)phenyl]propanoate | n/a | C25H25NO5 | 详情 | 详情 |
| (V) | 53341 | methyl (2S)-2-{[(benzyloxy)carbonyl]amino}-3-[4-(benzyloxy)-3-iodophenyl]propanoate | n/a | C25H24INO5 | 详情 | 详情 |
| (VI) | 53342 | 4,4,4',4',5,5,5',5'-Octamethyl-2,2'-bi-1,3,2-dioxaborolane; Bis(pinacolato)diboron; Diboron pinacol ester | 73183-34-3 | C12H24B2O4 | 详情 | 详情 |
| (VII) | 53343 | methyl (2S)-2-{[(benzyloxy)carbonyl]amino}-3-[4-(benzyloxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]propanoate | n/a | C31H36BNO7 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(V)The borinated tyrosine intermediate (VII) has been obtained as follows: The esterification of L-tyrosine (I) with SOCl2 and methanol gives the methyl ester (II), which is N-protected with Cbz-Cl and K2CO3 to yield the carbamate (III). The O-protection of (III) with benzyl bromide and Cs2CO3 affords the benzyl ether (IV), which is iodinated with I2 and Ag2SO4 to provide the 3-iodotyrosine derivative (V). Finally, the borylation of (V) by means of pinacolatodiborane (VI) catalyzed by PdCl2[bis(diphenylphosphanyl)ferrocene] (PdCl2(dppf)) gives rise to the target tyrosine intermediate (VII).
| 【1】 Lin, S.N.; Danishefsky, S.J.; The total synthesis of proteasome inhibitors TMC-95A and TMC-95B: Discovery of a new method to generate cis-propenyl amides. Angew Chem. Int Ed 2002, 41, 3, 512. |
| 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) | 48794 | (S)-(-)-Tyrosine; (S)-2-Amino-3-(4-hydroxyphenyl)propionic acid; 3-(4-Hydroxyphenyl)-L-alanine; L-(-)-Tyrosine; L-3-(4-Hydroxyphenyl)alanine; L-4-Hydroxy-17O-phenylalanine; L-beta-(p-Hydroxyphenyl)alanine; L-Hydroxy Phenyl Alanine; L-tyrosine | 60-18-4 | C9H11NO3 | 详情 | 详情 |
| (II) | 21431 | methyl (2S)-2-amino-3-(4-hydroxyphenyl)propanoate | 1080-06-4 | C10H13NO3 | 详情 | 详情 |
| (III) | 53339 | methyl (2S)-2-{[(benzyloxy)carbonyl]amino}-3-(4-hydroxyphenyl)propanoate | n/a | C18H19NO5 | 详情 | 详情 |
| (IV) | 53340 | methyl (2S)-2-{[(benzyloxy)carbonyl]amino}-3-[4-(benzyloxy)phenyl]propanoate | n/a | C25H25NO5 | 详情 | 详情 |
| (V) | 53341 | methyl (2S)-2-{[(benzyloxy)carbonyl]amino}-3-[4-(benzyloxy)-3-iodophenyl]propanoate | n/a | C25H24INO5 | 详情 | 详情 |
| (VI) | 53342 | 4,4,4',4',5,5,5',5'-Octamethyl-2,2'-bi-1,3,2-dioxaborolane; Bis(pinacolato)diboron; Diboron pinacol ester | 73183-34-3 | C12H24B2O4 | 详情 | 详情 |
| (VII) | 53343 | methyl (2S)-2-{[(benzyloxy)carbonyl]amino}-3-[4-(benzyloxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]propanoate | n/a | C31H36BNO7 | 详情 | 详情 |