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【结 构 式】 
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【分子编号】68108 【品名】2,3-Dimethyl-2,3-butanediol;2,3-Dimethylbutane-2,3-diol;Tetramethylethylene glycol;pinacol 【CA登记号】76-09-5 |
【 分 子 式 】C6H14O2 【 分 子 量 】118.17596 【元素组成】C 60.98% H 11.94% O 27.08% |
合成路线1
该中间体在本合成路线中的序号：(XX)The key intermediate (XIII) is prepared by N-protection of 5-bromopyrimidin-2-amine (XVI) with Boc2o by means of DMAP in DMF to give N,N-di-Boc-5-bromopyrimidin-2-amine (XVII), which by metalation with BuLi in THF, followed by borylation with (i-Pro)3B provides the pyrimidin-5-ylboronic acid derivative (XVIII). Hydrolysis of protected amine (XVIII) with methanolic HCl affords 2-aminopyrimidin-5-ylboronic acid (IV), which is finally cyclized with pinacol (XX) in refluxing toluene or xylene .
| 【1】 Xu, J., Lai, W., Yang, B., Gu, S. (Jiangsu ChemFuture Pharma Tech. Co., Ltd.). Synthesis method of 2-amino-5-pyridineboronic acid pinacol ester. Cn 102399235 |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIII) | 68102 | 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidin-2-amine | 402960-38-7 | C10H16BN3O2 | 详情 | 详情 |
| (XVI) | 34822 | 5-bromo-2-pyrimidinamine; 5-bromo-2-pyrimidinylamine | 7752-82-1 | C4H4BrN3 | 详情 | 详情 |
| (XVII) | 68105 | N,N-di-Boc-5-bromopyrimidin-2-amine;Imidodicarbonicacid, 2-(5-bromo-2-pyrimidinyl)-, 1,3-bis(1,1-dimethylethyl) ester;Imidodicarbonicacid, (5-bromo-2-pyrimidinyl)-, bis(1,1-dimethylethyl) ester (9CI);(5-Bromopyrimidin-2-yl)bis(tert-butoxycarbonyl)amine | 209959-33-1 | C14H20BrN3O4 | 详情 | 详情 |
| (XVIII) | 68106 | C14H22BN3O6 | 详情 | 详情 | ||
| (XIX) | 68107 | (2-aminopyrimidin-5-yl)boronic acid | C4H6BN3O2 | 详情 | 详情 | |
| (XX) | 68108 | 2,3-Dimethyl-2,3-butanediol;2,3-Dimethylbutane-2,3-diol;Tetramethylethylene glycol;pinacol | 76-09-5 | C6H14O2 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XVII)Intermediate (III) is prepared by protection of either 4-iodopyrazole (XIIIa) or 4-bromopyrazole (XIIIb) with ethyl vinyl ether (XIV) by means of HCl in toluene or CH2Cl2 to give the corresponding (1-ethoxyethyl)pyrazoles (XVa) and (XVb). Finally, pyrazole (XVa) is submitted to metal-halogen exchange by means of i-PrMgCl in THF, followed by condensation with isopropyl pinacol borate (XVI) (obtained by reaction of pinacol [XVII] with triisopropyl borate at reflux), or pyrazole (XVb) is condensed with methyl pinacol borate (XVIII) by means of i-PrMgCl·LiCl in THF .
| 【1】 Lin, Q., Meloni, D., Pan, Y. et al. Enantioselective synthesis of Janus kinase inhibitor INCB018424 via an organocatalytic aza-Michael reaction. Org Lett 2009, 11(9): 1999-2002. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIIIa) | 69178 | 4-iodopyrazole;4-Iodo-1H-pyrazole | 3469-69-0 | C3H3IN2 | 详情 | 详情 |
| (XIIIb) | 69179 | C3H3BrN2 | 详情 | 详情 | ||
| (XVa) | 69180 | 1-(1-ethoxyethyl)-4-iodo-1H-pyrazole | C7H11IN2O | 详情 | 详情 | |
| (XVb) | 69181 | 4-bromo-1-(1-ethoxyethyl)-1H-pyrazole | C7H11BrN2O | 详情 | 详情 | |
| (III) | 68071 | 1-(1-ethoxyethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole | C13H23BN2O3 | 详情 | 详情 | |
| (XIV) | 18762 | 1-Ethoxyethylene; Ethyl vinyl ether；Ethoxyethene | 109-92-2 | C4H8O | 详情 | 详情 |
| (XVI) | 67808 | Isopropyl pinacolyl borate;Isopropoxyboronic acid pinacol ester;2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 61676-62-8 | C9H19BO3 | 详情 | 详情 |
| (XVII) | 68108 | 2,3-Dimethyl-2,3-butanediol;2,3-Dimethylbutane-2,3-diol;Tetramethylethylene glycol;pinacol | 76-09-5 | C6H14O2 | 详情 | 详情 |
| (XVIII) | 69182 | Methoxyboronic acid pinacol ester;2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1195-66-0 | C7H15BO3 | 详情 | 详情 |