Synthesis of Alkyl Bis(trifluoromethyl)carbinols via Fe-LMCT-Enabled Hydrobis(trifluoromethyl)carbinolation of Alkenes.

Bis(trifluoromethyl)carbinols are valuable pharmacophores, yet their synthesis is challenging, largely due to a scarcity of safe and effective bis(trifluoromethyl)carbinolation reagents. Here, we realized the hydrobis(trifluoromethyl)carbinolation of alkenes, utilizing stable and readily accessible 2,2-bis(trifluoromethyl)glycolic acid as a source of both the bis(trifluoromethyl)carbinol unit and a hydrogen atom. This process leverages a photoinduced Fe-LMCT-enabled radical decarboxylation process that generates a key bis(trifluoromethyl)carbinol radical intermediate.

Photocatalyzed Selective Hydrocarbonation of Alkenes with Hantzsch Esters toward 4-Alkyl-Hantzsch Esters.

Here, we describe a mild photoredox-neutral reaction system that enables the selective hydrocarbonation of alkenes with Hantzsch esters, affording structurally diverse 4-alkyl-Hantzsch esters. This straightforward protocol can be performed under an air atmosphere without the need for any transition metals. The synthetic potential of this method is well exemplified by the late-stage structural modification of a series of pharmaceutically relevant complex molecules.

One-Carbon Ring Expansion of Indoles and Pyrroles: A Straightforward Access to 3-Fluorinated Quinolines and Pyridines.

3-Fluorinated quinolines and pyridines are prevalent pharmacophores, yet their synthesis is often challenging. Herein, we demonstrate that dibromofluoromethane as bromofluorocarbene source enables the one-carbon ring expansion of readily available indoles and pyrroles to structurally diverse 3-fluorinated quinolines and pyridines. This straightforward protocol requires only a short reaction time of ten minutes and can be performed under air atmosphere.