Catalytic Asymmetric and Stereoselective Synthesis of Vinylcyclopropanes

Abstract

The first sequential catalytic asymmetric carbolithiation reaction of dienyl systems followed by a 1,3-intramolecular elimination leads to (E)- and trans-disubstituted vinylcyclopropanes in moderate to good enantiomeric excesses.

carbometallation - (-)-sparteine - chirality - vinylcyclopropanes - asymmetric catalysis

References

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18

Typical Experimental Procedure for the Preparation of 13a from 7: A solution of acetal 7 (1 mmol) in hexane (5 mL) was added to the solution of n-butyllithium (3.3 mmol) in hexane in the presence of 10 mol% of (-)-sparteine (based on starting material) at -10 °C over a period of 20 min. When the carbolithiation reaction was complete (as followed by TLC), the orange reaction mixture was rapidly warmed to room temperature and stirred overnight. Then the reaction mixture was cooled to 0 °C, and an aqueous 1 N HCl solution (10 mL) was added. The organic phase was separated, and the aqueous layer was extracted twice with ether (2 × 10 mL). The combined organic layers were washed with water, dried over MgSO₄ and evaporated under reduced pressure (flask being immerged in an icewater bath). The residue was purified by column chromatography over silica gel (60-120 mesh, hexane) to give the desired compound 13a in 53% yield with an enantiomeric excess of 83%.

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A large excess of (1R, 2R)-N, N’-dimethyl-1,2-diphenylethanediamine was used in order to avoid any kinetic resolution. No starting material was left (see ref. [19] ).

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25

Specific rotations for vinylcyclopropane derivatives: 12a [α]_D ²⁵ = -13.33 (c 0.60, CHCl₃); 12b [α]_D ²⁵ = -11.66 (c 1.2, CHCl₃); 13a [α]_D ²⁵ = -46.6 (c 1.67, CHCl₃); 13b [α]_D ²⁵ = -23.3 (c 1.2, CHCl₃); 14a [α]_D ²⁵ = -25.45 (c 1.12, CHCl₃); 14b [α]_D ²⁵ = -17.5 (c 0.80, CHCl₃); 15a [α]_D ²⁵ = -8.24 (c 1.7, CHCl₃); 15b [α]_D ²⁵ = -7.69 (c 1.04, CHCl₃); 17 [α]_D ²⁵ = -20.0 (c 0.80, CHCl₃).