Making more efficient lithium carbenoid reagents for cyclopropanation by hetero-aggregation: A DFT prediction on a new factor to control the SN2-Type organometallic reaction

Lithium carbenoids are important reagents in organic synthesis. Systemic DFT calculations have been carried out to reveal the influence of hetero-aggregation states on the reactivity of lithium carbenoid reagents. The results indicate that the cyclopropanation reaction could be accelerated dramatically by hetero-aggregated lithium carbenoids with a halogen or oxygen as an α-heteroatom. The origin of the enhancement could attribute to the novel structural character of the hetero-aggregated lithium carbenoids. These intriguing finding predicts that it is practical to control a wide range of SN2-type organometallic reactions by using aggregated lithium carbenoids with other economical and convenient compounds.