|
【结 构 式】 
|
【分子编号】38319 【品名】(1R,3R)-2-benzyl-6,8-bis(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline; benzyl (1R,3R)-2-benzyl-6-(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether 【CA登记号】 |
【 分 子 式 】C46H47NO5 【 分 子 量 】693.88292 【元素组成】C 79.63% H 6.83% N 2.02% O 11.53% |
合成路线1
该中间体在本合成路线中的序号：(S)-(XXIII)The condensation of the isoquinoline intermediate (IX) with the naphthaleneboronic acid intermediate (XIX) by means of palladium tetrakis(triphenylphosphine) and NaHCO3 in refluxing ethanol/toluene gives a 5:4 mixture of the (S) and (R) atropaisomers (XXIII), which, without separation, are treated with methanolic HCl to eliminate the methoxymethyl protecting groups and yield a mixture of (S) and (R) (XXIV). The dimerization of this mixture by means of silver oxide in dichloromethane affords a mixture of the (R,R), (R,S) and (S,S) dimers (XXV), which is deprotected with H2 over Pd/C in methanol/dichloromethane and submitted to HPLC to obtain the target (R,S) atropaisomer.
| 【1】 Hoye, T.R.; et al.; Total synthesis of michellamines A-C, korupensamines A-D, and ancistrobrevine B. J Org Chem 1999, 64, 19, 7184. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (S)-(XXIV) | 37861 | 4-[(1R,3R)-2-benzyl-6,8-bis(benzyloxy)-1,3-dimethyl-1,2,3,4-tetrahydro-5-isoquinolinyl]-8-methoxy-6-methyl-1-naphthol | C44H43NO4 | 详情 | 详情 | |
| (S)-(XXIII) | 38319 | (1R,3R)-2-benzyl-6,8-bis(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline; benzyl (1R,3R)-2-benzyl-6-(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether | C46H47NO5 | 详情 | 详情 | |
| (R)-(XXIII) | 63435 | 2-benzyl-6,8-bis(benzyloxy)-5-[5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthyl]-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline; benzyl 2-benzyl-6-(benzyloxy)-5-[5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthyl]-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether | C46H47NO5 | 详情 | 详情 | |
| (R)-(XXIV) | 63438 | 4-{1,3-dimethyl-2-(phenylmethyl)-6,8-bis[(phenylmethyl)oxy]-1,2,3,4-tetrahydro-5-isoquinolinyl}-6-methyl-8-(methyloxy)-1-naphthalenol | C44H43NO4 | 详情 | 详情 | |
| (IX) | 37847 | benzyl (1R,3R)-2-benzyl-6-(benzyloxy)-5-iodo-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether; (1R,3R)-2-benzyl-6,8-bis(benzyloxy)-5-iodo-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline | C32H32INO2 | 详情 | 详情 | |
| (XIX) | 37856 | 5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthylboronic acid | C14H17BO5 | 详情 | 详情 | |
| (XXV) | 37862 | C88H82N2O8 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(S)-(XXIII)The condensation of the isoquinoline intermediate (IX) with the naphthaleneboronic acid intermediate (XIX) by means of palladium tetrakis(triphenylphosphine) and NaHCO3 in refluxing ethanol/toluene gives a 5:4 mixture of the (S) and (R) atropaisomers (XXIII), which, without separation, are treated with methanolic HCl to eliminate the methoxymethyl protecting groups and yield a mixture of (S) and (R) (XXIV). The debenzylation of this mixture by means of H2 over Pd/C in methanol/dichloromethane affords a mixture of the target (S-biar) compound, along with its (R-biar)-atropaisomer that are separated by HPLC.
| 【1】 Hoye, T.R.; et al.; Total synthesis of michellamines A-C, korupensamines A-D, and ancistrobrevine B. J Org Chem 1999, 64, 19, 7184. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (S)-(XXIV) | 37861 | 4-[(1R,3R)-2-benzyl-6,8-bis(benzyloxy)-1,3-dimethyl-1,2,3,4-tetrahydro-5-isoquinolinyl]-8-methoxy-6-methyl-1-naphthol | C44H43NO4 | 详情 | 详情 | |
| (S-biar) | 38308 | (1R,3R)-5-(4-hydroxy-5-methoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydro-6,8-isoquinolinediol | C23H25NO4 | 详情 | 详情 | |
| (S)-(XXIII) | 38319 | (1R,3R)-2-benzyl-6,8-bis(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline; benzyl (1R,3R)-2-benzyl-6-(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether | C46H47NO5 | 详情 | 详情 | |
| (R)-(XXIII) | 63435 | 2-benzyl-6,8-bis(benzyloxy)-5-[5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthyl]-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline; benzyl 2-benzyl-6-(benzyloxy)-5-[5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthyl]-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether | C46H47NO5 | 详情 | 详情 | |
| (R)-(XXIV) | 63438 | 4-{1,3-dimethyl-2-(phenylmethyl)-6,8-bis[(phenylmethyl)oxy]-1,2,3,4-tetrahydro-5-isoquinolinyl}-6-methyl-8-(methyloxy)-1-naphthalenol | C44H43NO4 | 详情 | 详情 | |
| (IX) | 37847 | benzyl (1R,3R)-2-benzyl-6-(benzyloxy)-5-iodo-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether; (1R,3R)-2-benzyl-6,8-bis(benzyloxy)-5-iodo-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline | C32H32INO2 | 详情 | 详情 | |
| (XIX) | 37856 | 5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthylboronic acid | C14H17BO5 | 详情 | 详情 |
合成路线3
该中间体在本合成路线中的序号：(S)-(XXIII)The condensation of the isoquinoline intermediate (IX) with the naphthaleneboronic acid intermediate (XIX) by means of palladium tetrakis(triphenylphosphine) and NaHCO3 in refluxing ethanol/toluene gives a 5:4 mixture of the (S) and (R) atropaisomers (XXIII), which, without separation, are treated with methanolic HCl to eliminate the methoxymethyl protecting groups and yield a mixture of (S) and (R) (XXIV). The debenzylation of this mixture by means of H2 over Pd/C in methanol/dichloromethane affords a mixture of the target (R-biar) compound, along with its (S-biar)-atropaisomer that are separated by HPLC.
| 【1】 Hoye, T.R.; et al.; Total synthesis of michellamines A-C, korupensamines A-D, and ancistrobrevine B. J Org Chem 1999, 64, 19, 7184. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (S)-(XXIV) | 37861 | 4-[(1R,3R)-2-benzyl-6,8-bis(benzyloxy)-1,3-dimethyl-1,2,3,4-tetrahydro-5-isoquinolinyl]-8-methoxy-6-methyl-1-naphthol | C44H43NO4 | 详情 | 详情 | |
| (R-biar) | 38308 | (1R,3R)-5-(4-hydroxy-5-methoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydro-6,8-isoquinolinediol | C23H25NO4 | 详情 | 详情 | |
| (S)-(XXIII) | 38319 | (1R,3R)-2-benzyl-6,8-bis(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline; benzyl (1R,3R)-2-benzyl-6-(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether | C46H47NO5 | 详情 | 详情 | |
| (R)-(XXIII) | 63435 | 2-benzyl-6,8-bis(benzyloxy)-5-[5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthyl]-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline; benzyl 2-benzyl-6-(benzyloxy)-5-[5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthyl]-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether | C46H47NO5 | 详情 | 详情 | |
| (R)-(XXIV) | 63438 | 4-{1,3-dimethyl-2-(phenylmethyl)-6,8-bis[(phenylmethyl)oxy]-1,2,3,4-tetrahydro-5-isoquinolinyl}-6-methyl-8-(methyloxy)-1-naphthalenol | C44H43NO4 | 详情 | 详情 | |
| (IX) | 37847 | benzyl (1R,3R)-2-benzyl-6-(benzyloxy)-5-iodo-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether; (1R,3R)-2-benzyl-6,8-bis(benzyloxy)-5-iodo-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline | C32H32INO2 | 详情 | 详情 | |
| (XIX) | 37856 | 5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthylboronic acid | C14H17BO5 | 详情 | 详情 |
合成路线4
该中间体在本合成路线中的序号：(S)-(XXIII)The condensation of the isoquinoline intermediate (IX) with the naphthaleneboronic acid intermediate (XIX) by means of palladium tetrakis(triphenylphosphine) and NaHCO3 in refluxing ethanol/toluene gives a 5:4 mixture of the (S) and (R) atropaisomers (XXIII), which, without separation, is submitted to debenzylation by means of H2 over Pd/C in methanol/dichloromethane affording a mixture of the target (S-biar) compound, along with its (R-biar)-atropaisomer that are separated by HPLC.
| 【1】 Hoye, T.R.; et al.; Total synthesis of michellamines A-C, korupensamines A-D, and ancistrobrevine B. J Org Chem 1999, 64, 19, 7184. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (S)-(XXIII) | 38319 | (1R,3R)-2-benzyl-6,8-bis(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline; benzyl (1R,3R)-2-benzyl-6-(benzyloxy)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether | C46H47NO5 | 详情 | 详情 | |
| (S-biar) | 38320 | (1R,3R)-5-(4,5-dimethoxy-7-methyl-1-naphthyl)-1,3-dimethyl-1,2,3,4-tetrahydro-6,8-isoquinolinediol | C24H27NO4 | 详情 | 详情 | |
| (R)-(XXIII) | 63435 | 2-benzyl-6,8-bis(benzyloxy)-5-[5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthyl]-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline; benzyl 2-benzyl-6-(benzyloxy)-5-[5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthyl]-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether | C46H47NO5 | 详情 | 详情 | |
| (IX) | 37847 | benzyl (1R,3R)-2-benzyl-6-(benzyloxy)-5-iodo-1,3-dimethyl-1,2,3,4-tetrahydro-8-isoquinolinyl ether; (1R,3R)-2-benzyl-6,8-bis(benzyloxy)-5-iodo-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline | C32H32INO2 | 详情 | 详情 | |
| (XIX) | 38316 | 4,5-dimethoxy-7-methyl-1-naphthylboronic acid | C13H15BO4 | 详情 | 详情 |