Dabco → Dimethyl 1,4,6,7-tetrahydropyrano[4,3-b]pyrrole-2,3-dicarboxylate

HRID 1473264

反応式

HRID 1473264 の反応式
[O:1]1[CH2:6][CH2:5][C:4](=[N:7]O)[CH2:3][CH2:2]1.[CH3:9][O:10][C:11]([C:13]#[C:14][C:15]([O:17][CH3:18])=[O:16])=[O:12].C1N2CCN(CC2)C1>C1(C)C=CC=CC=1>[NH:7]1[C:13]([C:11]([O:10][CH3:9])=[O:12])=[C:14]([C:15]([O:17][CH3:18])=[O:16])[C:3]2[CH2:2][O:1][CH2:6][CH2:5][C:4]1=2

参加物

5

反応物 3

HCID 9237DabcoHCID 12980Dimethyl acetylenedicarboxylateHCID 12298558N-(oxan-4-ylidene)hydroxylamine

生成物 1

HCID 117700715Dimethyl 1,4,6,7-tetrahydropyrano[4,3-b]pyrrole-2,3-dicarboxylate収率 22%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
165 °C

実験手順

A suspension of dihydro-2H-pyran-4(3H)-one oxime (7 g, 60.8 mmol), dimethylacetylene dicarboxylate (9.72 ml, 79 mmol), and DABCO (2.046 g, 18.24 mmol) in Toluene (27.5 ml) were heated to 165° C. After 2 h, the reaction mixture was cooled to ambient temperature, concentrated in vacuo and purified by ISCO (0-100% EtOAc-hexanes) to afford dimethyl 1,4,6,7-tetrahydropyrano[4,3-b]pyrrole-2,3-dicarboxylate (3.2 g, 13.38 mmol, 22.00% yield) as a yellow solid. The residue was dissolved in DMF (30 mL), and treated with Cs2CO3 (5.29 g, 16.23 mmol) and 4-fluorobenzyl bromide (2.023 ml, 16.23 mmol). After 2 h, the reaction mixture was partitioned between EtOAc and sat. aq. NH4Cl. The organic layer was washed with water, brine, dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by ISCO (0-50% EtOAc-hexanes; 120 g column) to afford dimethyl 1-(4-fluorobenzyl)-1,4,6,7-tetrahydropyrano[4,3-b]pyrrole-2,3-dicarboxylate (3.92 g, 11.29 mmol, 18.56% yield) as a yellow oil. LCMS (m/z) ES+=348 (M+1).

後処理

  1. temperaturethe reaction mixture was cooled to ambient temperature
  2. concentrationconcentrated in vacuo
  3. custompurified by ISCO (0-100% EtOAc-hexanes)

出典と根拠

ORDレコード
ord-661e15bc5dc7482c8a90bd0547efda7b
出典データセット
uspto-grants-2015_04
特許番号
US09012642B2

関連ノート

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