Taking advantage of lithium monohalocarbenoid intrinsic alpha-elimination in 2-MeTHF: controlled epoxide ring-opening en route to halohydrins

The intrinsic degradative alpha-elimination of Li carbenoids somehow complicates their use in synthesis as C1-synthons. Nevertheless, we herein report how boosting such an alpha-elimination is a straightforward strategy for accomplishing controlled ring-opening of epoxides to furnish the corresponding beta-halohydrins. Crucial for the development of the method is the use of the eco-friendly solvent 2-MeTHF, which forces the degradation of the incipient monohalolithium, due to the very limited stabilizing effect of this solvent on the chemical integrity of the carbenoid. With this approach, high yields of the targeted compounds are consistently obtained under very high regiocontrol and, despite the basic nature of the reagents, no racemization of enantiopure materials is observed.