Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095, USA.
Science. 2019 May 17;364(6441):681-685. doi: 10.1126/science.aaw4212.
Chemical synthesis typically relies on reactions that generate complexity through elaboration of simple starting materials. Less common are deconstructive strategies toward complexity-particularly those involving carbon-carbon bond scission. Here, we introduce one such transformation: the hydrodealkenylative cleavage of C(sp)-C(sp) bonds, conducted below room temperature, using ozone, an iron salt, and a hydrogen atom donor. These reactions are performed in nonanhydrous solvents and open to the air; reach completion within 30 minutes; and deliver their products in high yields, even on decagram scales. We have used this broadly functionality tolerant transformation to produce desirable synthetic intermediates, many of which are optically active, from abundantly available terpenes and terpenoid-derived precursors. We have also applied it in the formal total syntheses of complex molecules.
化学合成通常依赖于通过对简单起始原料进行精心设计来生成复杂性的反应。较少见的是针对复杂性的解构策略——特别是涉及碳-碳键断裂的策略。在这里，我们介绍了一种这样的转化：在低于室温的条件下，使用臭氧、铁盐和氢原子供体进行 C(sp)-C(sp)键的氢去烯丙基裂解。这些反应在非无水溶剂中进行并且可以在空气中进行；在 30 分钟内完成；并且即使在公斤级规模下也能以高收率得到产物。我们已经使用这种广泛官能团容忍的转化来从丰富的萜类和萜类衍生前体中生成所需的合成中间体，其中许多是光学活性的。我们还将其应用于复杂分子的正式全合成中。
