Marshall Jonathan L, Lehnherr Dan, Lindner Benjamin D, Tykwinski Rik R
Department of Chemistry, Gunning-Lemieux Chemistry Center, University of Alberta, Edmonton, AB, T6G 2G2, Canada.
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, 14853, USA.
Chempluschem. 2017 Jul;82(7):967-1001. doi: 10.1002/cplu.201700168.
Acenes, heteroacenes, conjugated polycyclic hydrocarbons, and polycyclic aromatic hydrocarbons (collectively referred to in this review as conjugated polycyclic molecules, CPMs) have fascinated chemists since they were first isolated and synthesized in the mid 19th century. Most recently, these compounds have shown significant promise as the active components in organic devices (e.g., solar cells, thin-film transistors, light-emitting diodes, etc.), and, since 2001, a plethora of publications detail synthetic strategies to produce CPMs. In this review, we discuss reductive aromatization, reductive dearomatization, and elimination/extrusion reactions used to form CPMs. After a brief discussion on early methods to synthesize CPMs, we detail the use of reagents used for the reductive (de)aromatization of precursors containing 1,4-diols/diethers, including SnCl and iodide (I ). Extension of these methods to carbomers and cumulenes is briefly discussed. We then describe low-valent metal species used to reduce endoxides to CPMs, and discuss the methods to directly reduce acenediones and acenones to the respective acene. In the final section, we describe methods used to affect aromatization to the desired CPM via extrusion of small, volatile molecules.
自19世纪中叶首次被分离和合成以来，并苯、杂并苯、共轭多环烃和多环芳烃（在本综述中统称为共轭多环分子，CPMs）一直吸引着化学家。最近，这些化合物作为有机器件（如太阳能电池、薄膜晶体管、发光二极管等）中的活性成分显示出巨大的潜力，并且自2001年以来，大量出版物详细介绍了制备CPMs的合成策略。在本综述中，我们讨论了用于形成CPMs的还原芳构化、还原脱芳构化以及消除/挤出反应。在简要讨论了早期合成CPMs的方法之后，我们详细介绍了用于含有1,4 - 二醇/二醚的前体的还原（脱）芳构化的试剂的使用，包括SnCl和碘化物（I）。简要讨论了将这些方法扩展到卡宾和累积烯烃的情况。然后我们描述了用于将内过氧化物还原为CPMs的低价金属物种，并讨论了将并苯二酮和并苯酮直接还原为相应并苯的方法。在最后一部分，我们描述了通过挤出小的挥发性分子来实现所需CPM芳构化的方法。
