Enantiomerically Pure Cyclopropylamines via C-B to C-N Conversion

Abstract

For the first time cyclopropyltrifluoroborates have been utilized to form cyclopropylamines in a one-pot procedure. The scope was not only demonstrated by successfully reacting various racemic cis- and trans-2-substituted cyclopropanes as well as azides, but also by applying the sequence to enantiomerically pure building blocks. An approach to tranylcypromine as well as belactosin A is outlined.

Key words

boron - cyclopropanes - asymmetric synthesis - cyclopropylamine

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General Procedure for the C-B to C-N Conversion
Under an atmosphere of dry nitrogen, the trifluoroborate 3 (1 equiv) was suspended in a mixture of toluene (10 mL/mmol trifluoroborate 3) and MeCN (2.5 mL/mmol trifluoroborate 3). Then, SiCl₄ (1 M in CH₂Cl₂, 2 equiv) was added at r.t. and stirred for 20 min. The corresponding azide 5 (1.4 equiv) was added and the reaction mixture was stirred at r.t. or 40 °C for 5-15 h (depending on the azide used). The reaction was quenched with H₂O (10 mL/mmol trifluoroborate 3), and the layers were separated. The organic layer was extracted with HCl (1 M; 5 × 10 mL/mmol trifluoroborate 3). The combined aqueous layers were strongly basified with aq KOH (40%). The amine was extracted with Et₂O (4 × 50 mL/mmol trifluoroborate 3). The combined ether layers were dried over Na₂CO₃. The solvent was removed under reduced pressure.