Compound 1

(1S,6R,7R,7aS)-N-Methylhexahydro-1H-1,6-epoxypyrrolizin-7-amine

From: An efficient synthesis of loline alkaloids

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InChIKey OPMNROCQHKJDAQ-FKSUSPILSA-N

Synonyms:
  • 2,4-Methano-4H-furo(3,2-b)pyrrol-3-amine, hexahydro-N-methyl-, (2R,3R,3aS,4S,6aS)-,
  • [2R-(2a,3a,3ab,4a,6ab)]-Hexahydro-N-methyl-2,4-methano-4H-furo[3,2-b]pyrrol-3-amine,
  • Methyl-N-depropionyldecorticasine,
  • (1R,3S,7S,8R)-N-Methyl-2-oxa-6-azatricyclo[4.2.1.0~3,7~]nonan-8-amine,
  • 2,4-methano-4H-furo[3,2-b]pyrrol-3-amine, hexahydro-N-methyl-, (2R,3R,3aS,6aS)-,
  • Festucine,
  • loline

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

A solution of 11 mg (0.046 mmol, 1 eq.) N-Boc temuline (17) in THF (5 mL) was degassed with N2 in a sonicator for 5 minutes, then treated with 275 μL (0.275 mmol, 6 eq., 1M solution in THF) LiAlH4 and refluxed for 8 h. The reaction mixture was quenched with 1M aq. NaOH (0.3 mL) and 0.5 g silica was added and concentrated in vacuo. The crude product was purified by flash column chromatography (CHCl3:MeOH:NH4OH = 10:4:1) and the resulting free base was treated with 3M HCl in methanol (2 mL) and concentrated in vacuo to yield 10 mg (0.044 mmol, 96%) loline ∙2HCl (1) as a yellow oil (one spot on TLC). TLC (CHCl3:MeOH:NH4OH = 9:3:0.5), Rf = 0.12 (KMnO4). 1H NMR (D2O, 400 MHz): δ= 4.82 (s, 1H), 4.80 (s, 1H), 4.75 (dd, J=2.3, 4.8 Hz, 1H), 4.26 (s, 1H), 4.15 (d, J=13.9 Hz, 1H), 3.82–3.76 (m, 1H), 3.76–3.70 (m, 1H), 3.60 (d, J=13.9 Hz, 1H), 2.83 (d, J=0.9 Hz, 3H), 2.42 (ddd, J=7.6, 10.0, 15.0 Hz, 1H), 2.31 (ddd, J=5.0, 8.4, 15.0 Hz, 1H). 13C NMR (CDCl3, 100 MHz): δ= 83.4, 74.0, 72.2, 66.0, 64.2, 58.2, 36.4, 36.1. [α]25 D + 5.4° (c= 0.31, H2O). HRMS (ESI) calcd for C8H14N2O [M+H]+: 155.1179; found: 155.1176.

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