🎉 𝐂𝐨𝐧𝐠𝐫𝐚𝐭𝐮𝐥𝐚𝐭𝐢𝐨𝐧𝐬 𝐭𝐨 𝐌𝐚𝐫𝐯𝐢𝐧 𝐏𝐚𝐫𝐚𝐬𝐫𝐚𝐦, 𝐉𝐨𝐬𝐡𝐮𝐚 𝐊. 𝐌𝐢𝐭𝐜𝐡𝐞𝐥𝐥, 𝐚𝐧𝐝 𝐜𝐨-𝐰𝐨𝐫𝐤𝐞𝐫𝐬 𝐨𝐧 𝐭𝐡𝐞𝐢𝐫 𝐧𝐞𝐰 𝐉𝐀𝐂𝐒 𝐩𝐮𝐛𝐥𝐢𝐜𝐚𝐭𝐢𝐨𝐧: “𝐏𝐡𝐨𝐭𝐨-𝐒𝐭𝐢𝐭𝐜𝐡𝐢𝐧𝐠 𝐨𝐟 𝐍𝐢𝐭𝐫𝐨𝐚𝐥𝐤𝐚𝐧𝐞𝐬 𝐯𝐢𝐚 𝐂𝐫𝐨𝐬𝐬-𝐃𝐞𝐧𝐢𝐭𝐫𝐚𝐭𝐢𝐯𝐞 𝐎𝐥𝐞𝐟𝐢𝐧𝐚𝐭𝐢𝐨𝐧”! doi.org/10.1021/jacs.6c06460 🔬 This study reports the first direct cross- and self-olefination of nitroalkanes under simple conditions using only a base and visible-light irradiation, providing an efficient route to sterically congested tri- and tetrasubstituted alkenes. Visible-light irradiation of in situ generated nitronates enabled cross-denitrative olefination through a unique photo-stitching process. A broad range of functionalized nitroalkanes, including carbonyl- and heterocycle-containing substrates, were well tolerated. 💡 The method provides a practical complement to classical olefination and alkene metathesis for the synthesis of highly substituted alkenes. Mechanistic studies revealed a photoinitiated radical-chain process in which nitronates act as photoreductants, followed by a photodriven β-elimination. This work establishes nitronates as versatile photoreductants and coupling partners, opening new opportunities for light-driven radical-mediated olefination. 🐝 We are pleased to see that some nitroalkane substrates used in this study were sourced from AmBeed. In the graphic below, the corresponding 𝗔𝗺𝗕𝗲𝗲𝗱 𝗖𝗮𝘁. 𝗡𝗼𝘀. are highlighted in orange. 𝗧𝗿𝘆 𝗔𝗺𝗕𝗲𝗲𝗱’𝘀 𝗻𝗶𝘁𝗿𝗼𝗮𝗹𝗸𝗮𝗻𝗲𝘀 𝗶𝗻 𝘆𝗼𝘂𝗿 𝗿𝗲𝘀𝗲𝗮𝗿𝗰𝗵. ambeed.com/search/StructureS… #AmBeed #JACS #OrganicChemistry #Nitroalkanes #Olefination #Photochemistry #VisibleLight #BuildingBlocks #ResearchTools #Paper #Chemistry