Реакция #71031

Уравнение реакции

n-BuLi

DMF

N2

2-methyl-2-thiophen-2-yl-[1,3]dioxolane

N,N,N′,N′-tetramethyl-ethylendiamine

→

5-(2-methyl-[1,3]dioxolan-2-yl)-thiophene-2-carbaldehyde

Растворители

hexane

THF

Условия реакции

Обработка

1. 1
   workup.ADDITIONwas added dropwise
2. 2
   ДругоеThe cooling bath was removed
3. 3
   workup.ADDITIONThe reaction mixture was poured on sat. aq. NaH4Cl (200 mL)
4. 4
   Экстракцияextracted with EA (2×200 mL)
5. 5
   Сушкаextracts were dried over MgSO4
6. 6
   Фильтрацияfiltered
7. 7
   Другоеthe solvent was removed under reduced pressure

Методика

In a flame dried round-bottomed flask equipped with a magnetic stir bar and under inert atmosphere (N2), to a solution of commercially available 2-methyl-2-thiophen-2-yl-[1,3]dioxolane (5.00 g, 28.49 mmol) in THF (145.0 mL) at −78° C. was added dropwise N,N,N′,N′-tetramethyl-ethylendiamine (4.41 mL, 29.06 mmol) followed by n-BuLi (18.14 mL of a 1.6M solution in hexane, 29.06 mmol), maintaining the temperature at −78° C. The reaction mixture was then stirred for 2 h at −78° C. before DMF (6.74 mL, 87.22 mmol) was added dropwise. The cooling bath was removed and the reaction mixture was stirred for 16 h. The reaction mixture was poured on sat. aq. NaH4Cl (200 mL) and extracted with EA (2×200 mL). The combined org. extracts were dried over MgSO4, filtered, and the solvent was removed under reduced pressure to give crude 5-(2-methyl-[1,3]dioxolan-2-yl)-thiophene-2-carbaldehyde as an yellow oil. LC-MS-conditions 02: tR=0.87 min; [M+AcCN]+=240.32. The crude material was dissolved, under inert atmosphere (N2) in MeOH (51.2 mL) and treated at 0° C., portionwise, over 20 min, with NaBH4 (1.35 g, 34.19 mmol in five equal portions). The reaction mixture was stirred for 45 min at rt. The reaction mixture was poured on water (90 mL) and the aq. layer was extracted with EA (2×225 mL). The combined org. extracts were dried over MgSO4, filtered, and the solvents were removed under reduced pressure. Purification of the residue by FC (50:50 hept-EA) gave the title compound: TLC:rf (50:50 hept-EA)=0.40. LC-MS-conditions 02: tR=0.73 min; [M+H]+=201.46.

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