Photodisulfidation of alkenes with linear disulfides: Reaction scope and kinetics
作者:Joshua T. Kamps、Shafer M. Soars、Nichloas J. Bongiardina、Benjamin D. Fairbanks、Christopher N. Bowman
DOI:10.1016/j.tet.2022.132683
日期:2022.3
compared to thiols, reduced shrinkage stress, and increased refractive index of the resulting materials. It was determined that vinyl ethers were the only alkenes capable of undergoing photodisulfidation under ambient conditions and in reasonable timescales. The reaction between vinyl ethers and disulfides performed well in a variety of solvents providing modest to excellent yields (100% for bis(1-methylacetate)
硫醇-烯和硫醇-炔光介导的共轭在研究和实践中受到了广泛关注。本文介绍了基于自由基介导的二硫化物和乙烯基醚的 1:1 反应的烯烃的光二硫化,这为硫醇-烯和硫醇-炔聚合物中所见的硫化物类型的形成提供了额外的途径。尽管形成了类似的键,但这种从二硫化物开始的方法预计比硫醇-烯和硫醇-炔反应具有优势,包括与硫醇相比延长二硫化物的保质期、降低收缩应力和提高所得材料的折射率。已确定乙烯基醚是唯一能够在环境条件和合理时间范围内进行光二硫化的烯烃。乙烯基醚和二硫化物之间的反应在各种溶剂中表现良好,为许多评估的二硫化物底物提供中等至优异的产率(双(1-甲基乙酸酯)二硫化物 (DSMA)/三乙二醇二乙烯基醚 (TEGDVE) 为 100%)。已确定光二硫化反应的机理涉及硫基自由基的自动传播循环,其添加到乙烯基醚的任一端以在最终产物中形成硫醚和硫缩醛键。最后,虽然反应速率比硫醇-烯反应慢,但在所探索的条件下,光二硫化反应进行得相对较快。