New Light-Driven Chemistry Speeds Up Drug and Chemical Manufacturing
Chemists have developed a sunlight-powered method to build complex molecules from simple alcohols and other cheap materials, eliminating the need for toxic metal catalysts. The technique works at room temperature and could accelerate production of pharmaceuticals and specialty chemicals while reducing costs and environmental hazards.
Originaltitel: β-Scission of Secondary Alcohols via Photosensitization: Synthetic Utilization and Mechanistic Insights
<p>An efficient metal-free photocatalytic method for the alkylation of alkenes using accessible aliphatic alcohols as redox auxiliaries is presented. C-centered radicals can be generated under mild conditions and subsequently employed in a C(sp(3))-C(sp(3)) bond-forming process, which overall provides a C1 tethering strategy of nucleophiles and electrophiles. The optimized conditions accommodate various electron-deficient alkenes and secondary/tertiary alcohols, with applications in late-stage functionalization of natural products and pharmaceutically relevant compounds. Mechanistic investigations revealed a complex mechanistic manifold, including non-PCET fragmentation and concerted/stepwise PCET. Even though the previously thought PCET type mechanism is compatible with our observations, the non-PCET mechanism most probably constitutes a main pathway.</p>