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Abstract  A highly stereocontrolled  syn ‐addition of silicon nucleophiles across cyclopropenes with two different geminal substituents at C3 is reported. Diastereomeric ratios are excellent throughout (d.r.≥98:2) and enantiomeric excesses usually higher than 90 %, even reaching 99 %. This copper‐catalyzed C−Si bond formation closes the gap of the direct synthesis of α‐chiral cyclopropylsilanes.

Copper‐Catalyzed Enantio‐ and Diastereoselective Addition of Silicon Nucleophiles to 3,3‐Disubstituted Cyclopropenes