Di Filippo Mara, Baumann Marcus
University College Dublin, School of Chemistry, Science Centre South, Belfield, Dublin 4, Ireland.
Org Biomol Chem. 2023 Apr 5;21(14):2930-2934. doi: 10.1039/d3ob00122a.
A highly regioselective route to complex carbocyclic scaffolds through a continuous photochemical process is reported. Crucially, we uncovered that substitutents on the right-hand aryl ring are placed away from a transient carbene species which induces the exclusive regioselectivity observed. By varying the non-symmetrically substituted aryl moiety, we demonstrate how the product outcome favors cyclobutenes for electron-poor and neutral substituents and cycloheptatrienes for more electron-rich systems. Additionally, a photochemically induced rearrangement was uncovered for highly electron-rich substrates that ultimately generates complex hydroperoxides. Overall, this facile one-step process is fast and high yielding and demonstrates the power of photochemistry towards the exploration of new chemical space.
报道了一种通过连续光化学过程合成复杂碳环骨架的高度区域选择性路线。至关重要的是，我们发现右手芳基环上的取代基远离诱导观察到的区域选择性的瞬态卡宾物种。通过改变非对称取代的芳基部分，我们展示了产物结果如何有利于贫电子和中性取代基生成环丁烯，而富电子体系则生成环庚三烯。此外，还发现了富电子底物的光化学诱导重排，最终生成复杂的氢过氧化物。总体而言，这种简便的一步过程快速且产率高，展示了光化学在探索新化学空间方面的力量。
