Stereoselective Ring-Opening of N-tert-Butanesulfinylaziridines: Access to Acetylenic α-Amino Alcohols

Abstract

Ring-opening of enantiopure trans and cis 2,3-disubstituted ethynyl N-tert-butanesulfinylaziridines by water under acidic conditions proved to be highly regio- and diastereoselective, leading to the corresponding enantiopure anti and syn acetylenic α-amino alcohols. The regio- and stereochemistries were unambiguously determined by NOE experiments through the formation of oxazol­idinone derivatives.

amino alcohols - asymmetric synthesis - aziridines - dia­stereoselectivity - regioselectivity

References and Notes

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15

Acetylenic α-Amino Alcohols 4a-g; Typical Procedure. A stirred solution of N-tert-butanesulfinylaziridines 3a-g (1.00 mmol) and PTSA monohydrate (190 mg, 1.00 mmol) in MeCN (40 mL) and H₂O (5.7 mL) was refluxed for 20 h. After cooling to r.t., a sat. aq solution of NaHCO₃ (40 mL) and CH₂Cl₂ (40 mL) were added and the resulting mixture was stirred for 15 min at r.t. The layers were then separated and the aqueous layer was extracted with CH₂Cl₂ (3 × 40 mL). The combined organic layers were washed with a sat. aq solution of NaHCO₃ (40 mL), dried over anhyd Na₂SO₄, and concentrated in vacuo. The residual oil was purified by flash chromatography over silica gel (CH₂Cl₂ → MeOH-CH₂Cl₂, 1:9) to first give regioisomers 5a-g and then the corresponding diastereo- and enantiomerically pure acetylenic α-amino alcohols 4a-g.

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