Dai Lei, Guo Jiami, Huang Qingqin, Lu Yixin
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, Fujian 350207, China.
Sci Adv. 2022 Sep 16;8(37):eadd2574. doi: 10.1126/sciadv.add2574. Epub 2022 Sep 14.
Alkynes represent a family of pivotal and sustainable feedstocks for various industries such as pharmaceuticals, agrochemicals, and materials, and they are widely used as important starting materials for the production of a broad range of chemical entities. Nevertheless, efficient structural elaborations of alkynes in chemical synthesis, especially asymmetric multifunctionalization of alkynes, remain largely unexplored. It is thus imperative to develop new asymmetric synthetic approaches, making use of these richly available chemical feedstocks, and enabling their conversion to value-added chiral molecules. Here, we disclose our findings on highly enantioselective multifunctionalization of alkynes by merging photochemistry and chiral phosphoric acid catalysis. Our reported one-pot synthetic protocol is applicable to all types of alkyne substrates, incorporating all three reactants in a fully atom-economic fashion to produce optically enriched tetrasubstituted triaryl- and diarylmethanes, important structural scaffolds in medicinal chemistry and biological sciences.
炔烃是制药、农用化学品和材料等各种行业关键且可持续的原料家族，它们被广泛用作生产多种化学实体的重要起始原料。然而，化学合成中炔烃的高效结构修饰，尤其是炔烃的不对称多官能化，在很大程度上仍未得到充分探索。因此，开发新的不对称合成方法势在必行，利用这些丰富可得的化学原料，并将其转化为增值手性分子。在此，我们通过结合光化学和手性磷酸催化，披露了关于炔烃高度对映选择性多官能化的研究结果。我们报道的一锅法合成方案适用于所有类型的炔烃底物，以完全原子经济的方式纳入所有三种反应物，以生产光学富集的四取代三芳基和二芳基甲烷，这是药物化学和生物科学中的重要结构骨架。
