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【结 构 式】 
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【分子编号】57211 【品名】(9aS,9bS)-5-[{5-[[(9aS,9bS)-5-oxooctahydro-5lambda~5~-dipyrrolo[1,2-c:2,1-e][1,3,2]diazaphosphol-5-yl](methyl)amino]pentyl}(methyl)amino]octahydro-5lambda~5~-dipyrrolo[1,2-c:2,1-e][1,3,2]diazaphosphol-5-one 【CA登记号】 |
【 分 子 式 】C23H44N6O2P2 【 分 子 量 】498.589124 【元素组成】C 55.41% H 8.89% N 16.86% O 6.42% P 12.42% |
合成路线1
该中间体在本合成路线中的序号：(VI)The alkylation of phenylacetylene (I) with AlMe3 and ZnCl2CP2 gives the alpha-methylstyrene (II), which is treated with paraformaldehyde and BuLi to yield 3-phenyl-2-buten-1-ol (III). The reaction of (III) with NCS and DMS affords the butenyl chloride (IV), which is treated with trichlorosilane, TEA and CuCl to provide the allylic trichlorosilane (V). The condensation of (V) with benzaldehyde (VI) by means of the chiral catalyst (VII) and tetrabutylammonium iodide in dichloromethane gives the chiral diphenylcarbinol (VIII), which is submitted to hydroboration by means of 9-BBN and NaBO3 to yield the diol (IX). The selective, two step reduction of one phenyl group of (IX) with H2 over Rh/alumina and H2 over Pt/C affords the chiral cyclohexyl-butanediol derivative (X), which is oxidized by means of (COCl)2, DMSO and TEA in dichloromethane to provide the keto-aldehyde (XI). Finally, this compound is reductocondensed with 1-(2-methoxyphenyl)piperazine (XII) by means of NaBH(OAc)3 in 1,2-dichloroethane to give the target disubstituted piperazine.
| 【1】 Denmark, S.E.; Fu, J.; Asymmetric construction of quaternary centers by enantioselective allylation: Application to the synthesis of the serotonin antagonist lY426965. Org Lett 2002, 4, 11, 1951. |
| 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) | 20597 | 1-ethynylbenzene | 536-74-3 | C8H6 | 详情 | 详情 |
| (II) | 28450 | 1-isopropenylbenzene | 98-83-9 | C9H10 | 详情 | 详情 |
| (III) | 57208 | (E)-3-phenyl-2-buten-1-ol | C10H12O | 详情 | 详情 | |
| (IV) | 57209 | 1-[(E)-3-chloro-1-methyl-1-propenyl]benzene | C10H11Cl | 详情 | 详情 | |
| (V) | 57210 | trichloro[(E)-3-phenyl-2-butenyl]silane | C10H11Cl3Si | 详情 | 详情 | |
| (VI) | 57211 | (9aS,9bS)-5-[{5-[[(9aS,9bS)-5-oxooctahydro-5lambda~5~-dipyrrolo[1,2-c:2,1-e][1,3,2]diazaphosphol-5-yl](methyl)amino]pentyl}(methyl)amino]octahydro-5lambda~5~-dipyrrolo[1,2-c:2,1-e][1,3,2]diazaphosphol-5-one | C23H44N6O2P2 | 详情 | 详情 | |
| (VII) | 10498 | Benzaldehyde;Benzoic aldehyde;Phenylmethanal | 100-52-7 | C7H6O | 详情 | 详情 |
| (VIII) | 57212 | (1S,2S)-2-methyl-1,2-diphenyl-3-buten-1-ol | C17H18O | 详情 | 详情 | |
| (IX) | 57213 | (1S,2S)-2-methyl-1,2-diphenyl-1,4-butanediol | C17H20O2 | 详情 | 详情 | |
| (X) | 57214 | (1S,2S)-1-cyclohexyl-2-methyl-2-phenyl-1,4-butanediol | C17H26O2 | 详情 | 详情 | |
| (XI) | 57215 | (3S)-4-cyclohexyl-3-methyl-4-oxo-3-phenylbutanal | C17H22O2 | 详情 | 详情 | |
| (XII) | 11882 | 1-(2-Methoxyphenyl)piperazine; Methyl 2-piperazinophenyl ether; 1-(2-Methoxyphenyl)-piperazine | 35386-24-4 | C11H16N2O | 详情 | 详情 |