Cheng Yuan-Yuan, Xu Jiawei, Lin Zhipeng, Li Yanjun, Ackermann Lutz
Wöhler Research Institute for Sustainable Chemistry (WISCh), Georg-August-Universität Göttingen, Tammannstraße 2, Göttingen, 37077, Germany.
Chemistry. 2024 Oct 23;30(59):e202402333. doi: 10.1002/chem.202402333. Epub 2024 Oct 7.
Cross-dehydrogenative couplings (CDC) present an efficient strategy for the assembly of biorelevant heterocycles, but are thus far largely limited to toxic transition metals and rather harsh reaction conditions. In sharp contrast, we, herein report on a mild photoelectrocatalyzed CDC-[4+2] annulation enabling the synthesis of functionalized isothiochromenes enabled by a proton-coupled electron transfer (PCET) strategy. The transformative photoelectrocatalysis obviated toxic transition-metal, high reaction temperatures, and stoichiometric chemical redox reagents. This approach was characterized by exceedingly mild conditions, ample substrate scope, and a commercially available catalyst. Gram-scale reactions and a telescoped synthesis route reflected the unique potential in the green synthesis of important S-heterocycles.
交叉脱氢偶联反应（CDC）为构建具有生物相关性的杂环提供了一种有效策略，但迄今为止，该反应主要局限于有毒的过渡金属以及相当苛刻的反应条件。与之形成鲜明对比的是，我们在此报道了一种温和的光电催化CDC-[4+2]环化反应，该反应通过质子耦合电子转移（PCET）策略实现了功能化异硫代色烯的合成。这种变革性的光电催化反应避免了使用有毒的过渡金属、高温反应以及化学计量的化学氧化还原试剂。该方法具有条件极为温和、底物范围广以及使用市售催化剂的特点。克级规模的反应和串联合成路线体现了其在绿色合成重要含硫杂环化合物方面的独特潜力。
