Cyclopropanation of Alkenes with Halodiazirines as Halocarbene Precursors in Continuous Flow.

The cyclopropanation reaction of alkenes with photolytically-generated chlorocarbenes from chlorodiazirines is reported as an effective way to prepare substituted 3-chloro-3-aryl-cyclopropanes. This practical and efficient approach allows the synthesis of various 3-chloro-3-aryl-cyclopropanes (32 examples) in continuous flow in 5-minute residence time under light-emitting diode (LED) irradiation. The conditions using 380 nm LED irradiation were successfully extended to the synthesis of substituted 3-bromo-3-aryl-cyclopropanes (3 examples).

Boric acid as a precatalyst for BH3-catalyzed hydroboration.

We report that boric acid, BO3H3, is a good precatalyst for the BH3-catalyzed hydroboration of esters using pinacolborane as a borylation agent. Using microwave irradiation as an energy source, we demonstrated that a dozen esters were converted into the corresponding boronate ethers in good yields. It was also possible to use boric acid as a precatalyst to reduce carbonates and alkynes. Considering the hazardous and pyrophoric nature of BH3 solutions, boric acid proves to be a safe and green precatalyst for the metal-free reduction of unsaturated species.