Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi 221 005, India.
J Org Chem. 2021 Apr 16;86(8):5908-5921. doi: 10.1021/acs.joc.1c00417. Epub 2021 Apr 6.
The unique properties of ketoximes are used prominently for the synthesis of heterocycles. In contrast, their potential to absorb light and photoelectron transfer processes remains challenging. Widespread interest in controlling direct excitation of ketoxime tacticity unlocks unconventional reaction pathways, enabling photochemical intramolecular skeletal modification to constitute alkynyl sulfides that cannot be realized via traditional activation. Despite decades of advancements, the alkynyl sulfides, particularly those composed of polar functionalities and derived from renewable sources, remain unknown. These findings demonstrate the importance of decelerated ketoxime from β-oxodithioester for the identification of reaction conditions. The method uses mild reaction conditions to generate excited-state photoreductant for the functionalization of an array of alkynyl sulfides. Additionally, a fundamental understanding of elementary steps using electrochemical and spectroscopic techniques/experiments revealed a PCET pathway to this transformation, while the involved substrates and their properties with improved economical tools indicated the translational potential of this method.
酮肟的独特性质在杂环合成中得到了广泛的应用。相比之下，它们在光吸收和光电子转移过程中的潜力仍然具有挑战性。广泛关注控制酮肟手性的直接激发，为开启非常规反应途径提供了可能，使光化学分子内骨架修饰能够构成不能通过传统激活实现的炔基硫化物。尽管已经取得了数十年的进展，但炔基硫化物，特别是那些由极性官能团组成且来自可再生资源的炔基硫化物，仍然未知。这些发现表明，从β-氧代二硫代酯中减速酮肟对于确定反应条件非常重要。该方法使用温和的反应条件生成激发态光还原剂，用于一系列炔基硫化物的功能化。此外，使用电化学和光谱技术/实验对基本步骤的深入了解揭示了这种转化的 PCET 途径，而涉及的底物及其具有改进的经济工具的性质表明了该方法的转化潜力。
