Zarkina Vesela G, Nichol Gary S, Cowley Michael J
EaSTCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, United Kingdom.
J Am Chem Soc. 2024 Aug 28;146(34):23680-23685. doi: 10.1021/jacs.4c07850. Epub 2024 Aug 14.
The incorporation of phosphorus and boron into [3]dendralenes provides access to heavy heterodendralenes, a new class of main-group precursor to "doped" polycyclic hydrocarbons. []Dendralenes are a core class of unsaturated hydrocarbons built from geminally connected polyenes; the resulting arrangement of conjugated C═C bonds enables []dendralenes to undergo reactions that allow rapid access to complex polycyclic compounds. The increasing technological and synthetic importance of main-group-containing polycyclic hydrocarbons and their analogues makes new routes to access such systems highly attractive. Here we report the preparation of the first heavy heterodendralenes in the form of phosphorus- and boron-containing [3]dendralenes, prepared by a ring-opening reaction of a 1,2-phosphaborete. We reveal the electronic effect of P/B incorporation and demonstrate that, like their hydrocarbon analogues, phosphabora[3]dendralenes undergo diene-transmissive cycloaddition chemistry.
将磷和硼引入[3]轮烯可得到重杂轮烯，这是一类新型的用于“掺杂”多环烃的主族前体。轮烯是由偕联多烯构建的一类核心不饱和烃；共轭C═C键的这种排列使轮烯能够发生反应，从而快速合成复杂的多环化合物。含主族元素的多环烃及其类似物在技术和合成方面的重要性日益增加，使得获取此类体系的新途径极具吸引力。在此，我们报告了首例以含磷和硼的[3]轮烯形式存在的重杂轮烯的制备，该化合物通过1,2-磷硼环丁烷的开环反应制备而成。我们揭示了磷/硼引入的电子效应，并证明磷硼[3]轮烯与它们的烃类类似物一样，能发生双烯传递环加成反应。
