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【结 构 式】 
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【分子编号】19021 【品名】(1R,4S)-4-[1-(Methanesulfonyloxy)-1-[4-(3-methyl-2-butenyloxy)phenyl]methyl]-2-methyldispiro[2,5-diazabicyclo[3,2,1]octane-6,1'-cyclohexane-4',2''-[1,3]-dioxolan]-3-one 【CA登记号】 |
【 分 子 式 】C27H38N2O7S 【 分 子 量 】534.674 【元素组成】C 60.65% H 7.16% N 5.24% O 20.95% S 6% |
合成路线1
该中间体在本合成路线中的序号：(XVII)Mesylation of either isomer, followed by elimination in mesylate (XVII) with potassium tert-butoxide gave enone (XVIII). Reduction of carbonyl group was then effected with AlH3, prepared from lithium aluminum hydride and aluminum chloride yielding (XIX), and finally, deprotection of acetal (XIX) with HCl in acetone afforded the desired compound.
| 【1】 Nagumo, S.; et al.; Total synthesis of antimuscarinic alkaloid, (±)-TAN1251A. Tetrahedron 2002, 58, 24, 4917. |
| 【2】 Nagumo, S.; et al.; Total synthesis of (±)-TAN1251A. Tetrahedron Lett 1998, 39, 25, 4493. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XVI) | 19020 | (1R,4S)-4-[1-Hydroxy-1-[4-(3-methyl-2-butenyloxy)phenyl]methyl]-2-methyldispiro[2,5-diazabicyclo[3,2,1]octane-6,1'-cyclohexane-4',2''-[1,3]-dioxolan]-3-one | C26H36N2O5 | 详情 | 详情 | |
| (XVII) | 19021 | (1R,4S)-4-[1-(Methanesulfonyloxy)-1-[4-(3-methyl-2-butenyloxy)phenyl]methyl]-2-methyldispiro[2,5-diazabicyclo[3,2,1]octane-6,1'-cyclohexane-4',2''-[1,3]-dioxolan]-3-one | C27H38N2O7S | 详情 | 详情 | |
| (XVIII) | 19022 | (1R,4S)-2-Methyl-4-[4-(3-methyl-2-butenyloxy)benzylidene]dispiro[2,5-diazabicyclo[3,2,1]octane-6,1'-cyclohexane-4',2''-[1,3]-dioxolan]-3-one | C26H34N2O4 | 详情 | 详情 | |
| (XIX) | 19023 | (1R,4S)-2-Methyl-4-[4-(3-methyl-2-butenyloxy)benzylidene]dispiro[2,5-diazabicyclo[3,2,1]octane-6,1'-cyclohexane-4',2''-[1,3]-dioxolane] | C26H36N2O3 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XVIII)The reaction of aldol (XVII) with Ms-Cl and TEA in dichloromethane gives the mesylate (XVIII), which is treated with tBu-OK in THF to obtain the unsaturated amide (XIX). The reduction of the amide group of (XIX) with AlH3 in ethyl ether yields the corresponding unsaturated enamine (XX), which is finally deprotected by treatment with HCl in acetone.
| 【1】 Basak, A.; Wardrop, D.J.; N-methoxy-N-acylnitrenium ions: Application to the formal synthesis of (-)-TAN1251A. Org Lett 2001, 3, 7, 1053. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XVII) | 19020 | (1R,4S)-4-[1-Hydroxy-1-[4-(3-methyl-2-butenyloxy)phenyl]methyl]-2-methyldispiro[2,5-diazabicyclo[3,2,1]octane-6,1'-cyclohexane-4',2''-[1,3]-dioxolan]-3-one | C26H36N2O5 | 详情 | 详情 | |
| (XVIII) | 19021 | (1R,4S)-4-[1-(Methanesulfonyloxy)-1-[4-(3-methyl-2-butenyloxy)phenyl]methyl]-2-methyldispiro[2,5-diazabicyclo[3,2,1]octane-6,1'-cyclohexane-4',2''-[1,3]-dioxolan]-3-one | C27H38N2O7S | 详情 | 详情 | |
| (XIX) | 48807 | C26H34N2O4 | 详情 | 详情 | ||
| (XX) | 48808 | C26H36N2O3 | 详情 | 详情 |