Regio-Reversed α-Addition of Oxygen-Centered Nucleophiles to Carbazole-Based Trifluoromethyl Alkenes.

The conjugate addition of nucleophiles to electron-deficient alkenes represents one of the most powerful methods for forming chemical bonds. While this process typically demonstrates β-selectivity, the regio-reversed α-additions have largely been underexplored. In this study, we present an unprecedented α-specific nucleophilic addition of weak oxygen-centered nucleophiles to carbazole-based trifluoromethyl alkenes, achieved through a photoinduced polarity transduction pathway under mild, photocatalyst-free conditions. This reaction exhibits a broad scope, good functional group tolerance, exceptional α-regioselectivity and allows for late-stage skeletal diversification and polymer modification.