The direct and selective coupling of benzenes with aliphatic hydrocarbons is a promising strategy for C(sp²)-C(sp³) bond formation using readily available starting materials, yet it remains a significant challenge. In this study, we have developed a simplified photochemical system that incorporates catalytic amounts of iron(III) halides as multifunctional reagents and air as a green oxidant to address this synthetic problem. Under mild conditions, the reaction between a strong C(sp²)-H bond and a robust C(sp³)-H bond has been achieved, affording a broad range of cross-coupling products with high yields and commendable chemo-, site-selectivity. The iron halide acts as a multifunctional reagent that responds to visible light, initiates C-centered radicals, induces single-electron oxidation to carbocations, and participates in a subsequent Friedel-Crafts-type process. The gradual release of radical species and carbocation intermediates appears to be critical for achieving desirable reactivity and selectivity. This eco-friendly, cost-efficient approach offers access to various building blocks from abundant hydrocarbon feedstocks, and demonstrates the potential of iron halides in sustainable synthesis.

苯与脂肪烃的直接选择性偶联是使用易于获得的起始材料形成 C(sp ² )-C(sp ³ ) 键的一种有前途的策略，但它仍然是一个重大挑战。在这项研究中，我们开发了一种简化的光化学系统，该系统结合了催化量的卤化铁作为多功能试剂和空气作为绿色氧化剂来解决这一合成问题。^{在温和的条件下，实现了强C(sp 2} )-H键和强C(sp ³ )-H键之间的反应，提供了广泛的交叉偶联产物，具有高产率和值得称赞的化学位点-选择性。卤化铁作为多功能试剂，响应可见光，引发以C为中心的自由基，诱导单电子氧化为碳正离子，并参与随后的弗里德尔-克拉夫茨型过程。自由基物质和碳正离子中间体的逐渐释放似乎对于实现所需的反应性和选择性至关重要。这种环保、经济高效的方法可以从丰富的碳氢化合物原料中获取各种构建模块，并展示了卤化铁在可持续合成中的潜力。