福州大学宋秋玲团队报道了硼化苯二乙基乙烯的合成与转化解锁多种π键富集框架。相关研究成果发表在2024年3月27日出版的《美国化学会杂志》。

π键富集框架不仅是有机合成中的关键组成部分，而且由于其独特的结构特征，在材料科学、生物医学、光化学和其他相关学科领域发挥着关键作用。各种取代基与四取代烯烃中C═C双键的结合是目前一个非常重要的研究领域。然而，合成双键上具有不同取代基的四取代烯烃对实现立体选择性提出了重大挑战。

该文中，研究人员报道了一种有效且收敛的Cu催化的对称和不对称1,3-二炔、B2pin2和溴化乙炔的硼烷基化路线，以构建具有优异化学、立体和区域选择性的硼化苯基二乙炔（BPDEE）衍生物。

BPDEE衍生物可以通过分步过程转化为新的四取代有机π共轭宝石二苯二乙烯（DPDEE）、乙烯基苯基二乙烯（VPDEE）和苯基三乙乙烯（PTEE）衍生物，为合成以前难以合成的复杂π键富集框架提供了一个灵活的平台。

初步的光学表征表明，合成的分子具有聚集诱导发射（AIE）特性，这为未来的应用奠定了基础，丰富和推进了功能π-共轭框架的研究领域。

附：英文原文

Title: Unlocking Diverse π-Bond Enrichment Frameworks by the Synthesis and Conversion of Boronated Phenyldiethynylethylenes

Author: Jinhui Xie, Wangyang Li, Yong Lu, Yanping Zheng, Yanying Huang, Shanglin Chen, Qiuling Song

Issue&Volume: March 27, 2024

Abstract: The π-bond enrichment frameworks not only serve as a crucial building block in organic synthesis but also assume a pivotal role in the fields of materials science, biomedicine, photochemistry, and other related disciplines owing to their distinctive structural characteristics. The incorporation of various substituents into the C═C double bonds of tetrasubstituted alkenes is currently a highly significant research area. However, the synthesis of tetrasubstituted alkenes with diverse substituents on double bonds poses a significant challenge in achieving stereoselectivity. Here, we reported an efficient and convergent route of Cu-catalyzed borylalkynylation of both symmetrical and unsymmetrical 1,3-diynes, B2pin2, and acetylene bromide to the construction of boronated phenyldiethynylethylene (BPDEE) derivatives with excellent chemo-, stereo-, and regioselectivities. BPDEE derivatives could transform into novel tetrasubstituted organic π-conjugated gem-diphenyldiethynylethylene (DPDEE), vinylphenyldiethynylethylene (VPDEE), and phenyltriethynylethylene (PTEE) derivatives by a stepwise process, which provides a flexible platform for the synthesis of complex π-bond enrichment frameworks that were difficult to synthesize by previous methods. The initial optical characterization revealed that the synthesized molecules exhibited aggregation-induced emission (AIE) properties, which further establishes the groundwork for future applications and enriches and advances the field of functional π-conjugated frameworks research.

DOI: 10.1021/jacs.4c01989

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c01989