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

HRID 1473264

반응식

HRID 1473264 반응식
[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

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 1140Toluene용매

반응 조건

온도
165 °C

실험 절차

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).

후처리

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

출처 및 근거

ORD 기록
ord-661e15bc5dc7482c8a90bd0547efda7b
출처 데이터셋
uspto-grants-2015_04
특허 번호
US09012642B2

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