Hernandez Jackson J, Lawrie Alexandra P, Frontier Alison J
Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, New York 14611, United States.
J Org Chem. 2023 Dec 1;88(23):16065-16075. doi: 10.1021/acs.joc.3c01305. Epub 2023 Nov 16.
This article is a comprehensive report describing our studies in the field of aza-alkynyl Prins chemistry, comparing and contrasting the different reaction partners and reactivities observed during method development. The synthetic strategies combine an alkynyl aza-Prins coupling with an annulation, enabling the preparation of different nitrogen-containing heterocycles. Different iminium ions are explored as viable electrophiles for an alkynyl Prins cyclization, terminated by capture with a halogen nucleophile to form a vinyl halide. The synthetic utility of this functional handle is exploited through a number of Suzuki cross-couplings, allowing for the preparation of a modest library of compounds. In most cases, the Prins couplings are highly selective for the vinyl halides with geometry, resulting from anti-addition across the alkyne.
本文是一篇全面的报告，描述了我们在氮杂炔基普林斯化学领域的研究，比较和对比了方法开发过程中观察到的不同反应伙伴和反应活性。合成策略将炔基氮杂普林斯偶联与环化反应相结合，能够制备不同的含氮杂环化合物。探索了不同的亚胺离子作为炔基普林斯环化反应中可行的亲电试剂，通过用卤素亲核试剂捕获来终止反应，形成卤代乙烯。通过一系列铃木交叉偶联反应利用了这种官能团的合成效用，从而制备了一个适度的化合物库。在大多数情况下，普林斯偶联反应对具有特定几何构型的卤代乙烯具有高度选择性，这是由于炔烃上的反式加成所致。
