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【结 构 式】 
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【分子编号】45426 【品名】(2S,3R,4E)-2-allyl-1-[(4S)-4-benzyl-2-thioxo-1,3-oxazolidin-3-yl]-3-hydroxy-4-hexen-1-one 【CA登记号】 |
【 分 子 式 】C19H23NO3S 【 分 子 量 】345.46256 【元素组成】C 66.06% H 6.71% N 4.05% O 13.89% S 9.28% |
合成路线1
该中间体在本合成路线中的序号：(XVIII)Alternatively, the (R,R)-5-(hydroxymethyl)-2-cyclopenten-1-ol (VII) can also be obtained as follows: The condensation of the chiral oxazolidinethione (XV) with the pentenoic anhydride (II) by means of n-BuLi in THF gives the N-pentenoyloxazolidinethione (XVI), which is condensed with crotonaldehyde (XVII) catalyzed by TiCl4 and (-)-spartein in dichloromethane, yielding the chiral adduct (XVIII). The ring-closing metathesis of (XVIII) by means of a Ru catalyst in dichloromethane affords the chiral cyclopentenol derivative (XIX), which is reduced to the target diol (VII) by means of LiBH4 in THF.
| 【1】 Crimmins, M.T.; et al.; An efficient, general asymmetric synthesis of carbocyclic nucleosides: Application of an asymmetric aldol/ring-closing metathesis strategy. J Org Chem 2000, 65, 25, 8499. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (II) | 17666 | 1,1-dimethylpropionic 4-pentenoic anhydride | C10H16O3 | 详情 | 详情 | |
| (VII) | 17671 | (1R,5R)-5-(hydroxymethyl)-2-cyclopenten-1-ol | C6H10O2 | 详情 | 详情 | |
| (XV) | 45425 | (4S)-4-benzyl-1,3-oxazolidine-2-thione | C10H11NOS | 详情 | 详情 | |
| (XVI) | 41704 | 1-[(4R)-4-benzyl-2-thioxo-1,3-oxazolidin-3-yl]-4-penten-1-one | C15H17NO2S | 详情 | 详情 | |
| (XVII) | 22517 | (E)-2-butenal | 4170-30-3 | C4H6O | 详情 | 详情 |
| (XVIII) | 45426 | (2S,3R,4E)-2-allyl-1-[(4S)-4-benzyl-2-thioxo-1,3-oxazolidin-3-yl]-3-hydroxy-4-hexen-1-one | C19H23NO3S | 详情 | 详情 | |
| (XIX) | 45427 | [(4S)-4-benzyl-2-thioxo-1,3-oxazolidin-3-yl][(1S,2R)-2-hydroxy-3-cyclopenten-1-yl]methanone | C16H17NO3S | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XXII)Alternatively, 5(R)-(hydroxymethyl)-2-cyclopenten-1(R)-ol (VII) can also be obtained as follows: Acylation of the chiral oxazolidinethione (XIX) with the mixed anhydride (II) by means of BuLi in THF gives the N-pentenoyl-oxazolidinethione (XX), which by condensation with crotonaldehyde (XXI) catalyzed by TiCl4 and ()-spartein in dichloromethane yields the chiral adduct (XXII). The ring-closing metathesis of (XXII) by means of the ruthenium catalyst in dichloromethane affords the chiral cyclopentenol derivative (XXIII), which is reduced to the target diol (VII) by means of LiBH4 in THF.
| 【1】 Crimmins, M.T.; et al.; An efficient, general asymmetric synthesis of carbocyclic nucleosides: Application of an asymmetric aldol/ring-closing metathesis strategy. J Org Chem 2000, 65, 25, 8499. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (II) | 17666 | 1,1-dimethylpropionic 4-pentenoic anhydride | C10H16O3 | 详情 | 详情 | |
| (VII) | 17671 | (1R,5R)-5-(hydroxymethyl)-2-cyclopenten-1-ol | C6H10O2 | 详情 | 详情 | |
| (XIX) | 45425 | (4S)-4-benzyl-1,3-oxazolidine-2-thione | C10H11NOS | 详情 | 详情 | |
| (XX) | 41704 | 1-[(4R)-4-benzyl-2-thioxo-1,3-oxazolidin-3-yl]-4-penten-1-one | C15H17NO2S | 详情 | 详情 | |
| (XXI) | 22517 | (E)-2-butenal | 4170-30-3 | C4H6O | 详情 | 详情 |
| (XXII) | 45426 | (2S,3R,4E)-2-allyl-1-[(4S)-4-benzyl-2-thioxo-1,3-oxazolidin-3-yl]-3-hydroxy-4-hexen-1-one | C19H23NO3S | 详情 | 详情 | |
| (XXIII) | 45427 | [(4S)-4-benzyl-2-thioxo-1,3-oxazolidin-3-yl][(1S,2R)-2-hydroxy-3-cyclopenten-1-yl]methanone | C16H17NO3S | 详情 | 详情 |