Diethyl Ether → tert-butyl (1S)-1-formyl-2-methylpropyl(methyl)carbamate

HRID 2105118노트

반응식

HRID 2105118 반응식
[H-].[Al+3].[Li+].[H-].[H-].[H-].CON(C)[C:10](=[O:24])[C@H:11]([CH:21]([CH3:23])[CH3:22])[N:12]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH3:13].S([O-])(O)(=O)=O.[K+].C(OCC)C>C1COCC1.O>[C:14]([N:12]([CH3:13])[C@H:11]([CH:10]=[O:24])[CH:21]([CH3:22])[CH3:23])([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15]

참가 물질

7

반응물 4

HCID 3283Diethyl EtherHCID 516920Potassium bisulfateHCID 10446035Nalpha-Boc-Nalpha-methyl-l-valine N-methoxy-N-methylamideHCID 21226445Aluminium lithium hydride

생성물 1

HCID 10353241tert-butyl (1S)-1-formyl-2-methylpropyl(methyl)carbamate수율 92%

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매

실험 절차

Lithium aluminum hydride (875 mg, 23 mmol) was added to a solution of Nα-Boc-Nα-methyl-L-valine N-methoxy-N-methylamide (12) (2.0 g, 7.7 mmol) in dry THF (8 mL) and the reaction mixture was stirred for 20 min. The mixture was poured into a stirring solution of potassium hydrogen sulfate (3.14 g, 23 mmol) in water (100 mL). Diethyl ether (75 mL) was added, the layers separated and the aqueous layer extracted with diethyl ether (3×50 mL). The organic layers were combined, and washed sequentially with 3 N hydrochloric acid (3×30 mL), saturated aqueous sodium hydrogen carbonate (3×30 mL), and saturated aqueous sodium chloride (3×30 mL). The organic layer was dried with magnesium sulfate and the solvent was evaporated to yield the crude aldehyde 13 (1.52 g, 92% yield). Aldehyde 13 was used without further purification. Note: 13 can be stored under argon for ˜2 weeks, but when stored in organic solvents at room temperature, undergoes slow decomposition. 1H-NMR (200 MHz, CDCl3) 0.73 (d, J=6.9 Hz, 3H, CH3), 0.91 (d, J=6.9 Hz, 3H, CH3), 1.27 (s, 9H, Boc-(CH3)3), 2.02-2.15 (m, 1H, CH), 2.63 (s, 2H, NCH3), 2.72 (s, 1H, NCH3), 3.44 (d, J=9.5 Hz, 0.5H, CH), 3.86 (d, J=9 Hz, 0.5H, CH), 9.45 (s, 1H, CH); Exact mass calc'd for C11H22NO3 (M+H)+: 216.15997; Found (DCI): 216.15996; Optical rotation obtained was [α]D25 −104.2 (c 5.5, CHCl3).

후처리

  1. customthe layers separated
  2. extractionthe aqueous layer extracted with diethyl ether (3×50 mL)
  3. washwashed sequentially with 3 N hydrochloric acid (3×30 mL), saturated aqueous sodium hydrogen carbonate (3×30 mL), and saturated aqueous sodium chloride (3×30 mL)
  4. dry with materialThe organic layer was dried with magnesium sulfate
  5. customthe solvent was evaporated

출처 및 근거

ORD 기록
ord-80a19b33db8745bf9c41e8abab037094
출처 데이터셋
uspto-grants-2009_08
특허 번호
US07579323B1

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