Synthesis of new enantiopure trans-3,4-diaminocaranes from (+)-3-carene

A synthetic strategy to obtain new enantiopure trans-3,4-diaminocaranes derived from (+)-3-carene via a stereoselective methodology is described. The stereoselective preparation of 3,4-α-carene- or 3,4-β-carene-epoxide is followed by a ring opening by sodium azide to obtain the azido-alcohols. Subsequent cyclization affords the corresponding aziridine diastereoisomers, which are converted to azido amines by opening of the aziridine rings by sodium azide and then reduced to the final diamine diastereoisomers. The absolute configurations of the final diamines and of novel intermediates are established by 1H NMR spectra correlated with conformational analysis supported by molecular modeling.

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(1S,3R,4S,6R)-3,4-Aza-3,7,7-trimethylbicyclo-[4.1.0]-heptaneC10H17N[α]D20=+42.7 (c 0.31, CHCl3)Absolute configuration: (1S,3R,4S,6R)Source of chirality: (+)-3-carene

(1S,3R,4R,6R)-4-Azido-3,7,7-trimethylbicyclo[4.1.0]heptan-3-amineC10H18N4[α]D20=-40.5 (c 0.31, CHCl3)Absolute configuration: (1S,3R,4R,6R)Source of chirality: (+)-3-carene

(1R,3S,4S,6S)-4-Azido-4,7,7-trimethylbicyclo[4.1.0]heptan-3-amineC10H18N4[α]D20=+37.7 (c 0.28, CHCl3)Absolute configuration: (1S,3S,4S,6S)Source of chirality: (+)-3-carene

(1S,3R,4R,6R)-3,7,7-Trimethylbicyclo[4.1.0]heptane-3,4-diamineC10H20N2[α]D20=-12.3 (c 0.29, CHCl3)Absolute configuration: (1S,3R,4R,6R)Source of chirality: (+)-3-carene

(1S,3R,4R,6R)-4-Azido-3,7,7-trimethylbicyclo[4.1.0]heptan-3-olC10H17N3O[α]D20=-26.2 (c 0.20, CHCl3)Absolute configuration: (1S,3R,4R,6R)Source of chirality: (+)-3-carene

(1R,3S,4S,6S)-4-Azido-4,7,7-trimethylbicyclo[4.1.0]heptan-3-olC10H17N3O[α]D20=+93.4 (c 0.31, CHCl3)Absolute configuration: (1R,3S,4S,6S)Source of chirality: (+)-3-carene

(1S,3S,4R,6R)-3,4-Aza-3,7,7-trimethylbicyclo-[4.1.0]heptaneC10H17N[α]D20=+21.0 (c 0.40, CHCl3)Absolute configuration: (1S,3S,4R,6R)Source of chirality: (+)-3-carene

(1R,3R,4R,6S)-4-Azido-4,7,7-trimethylbicyclo[4.1.0]heptan-3-amineC10H18N4[α]D20=-74.2 (c 0.21, CHCl3)Absolute configuration: (1R,3R,4R,6S)Source of chirality: (+)-3-carene

(1S,3S,4S,6R)-4-Azido-3,7,7-trimethylbicyclo[4.1.0]heptan-3-amineC10H18N4[α]D20=+138.8 (c 0.27, CHCl3)Absolute configuration: (1S,3S,4S,6R)Source of chirality: (+)-3-carene

(1S,3R,4R,6R)-3,7,7-Trimethylbicyclo[4.1.0]heptane-3,4-diamineC10H20N2[α]D20=-12.3 (c 0.29, CHCl3)Absolute configuration: (1S,3R,4R,6R)Source of chirality: (+)-3-carene

(1S,3S,4S,6R)-3,7,7-Trimethylbicyclo[4.1.0]heptane-3,4-diamineC10H20N2[α]D20=+33.3 (c 0.47, CHCl3)Absolute configuration: (1S,3S,4S,6R)Source of chirality: (+)-3-carene