Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.
School of Chemistry and Chemical Engineering, Liaoning Normal University, 850 Huanghe Road, Dalian 116029, China.
Chem Soc Rev. 2021 Mar 1;50(4):2582-2625. doi: 10.1039/d0cs00283f.
Ynamides are unique alkynes with a carbon-carbon triple bond directly attached to the nitrogen atom bearing an electron-withdrawing group. The alkyne is strongly polarized by the electron-donating nitrogen atom, but its high reactivity can be finely tempered by the electron-withdrawing group. Accordingly, ynamides are endowed with both nucleophilic and electrophilic properties and their chemistry has been an active research field. The catalytic intermolecular annulations of ynamides, featuring divergent assembly of structurally important amino-heterocycles in a regioselective manner, have gained much attention over the past decade. This review aims to provide a comprehensive summary of the advances achieved in this area involving transition metal and acid catalysis. Moreover, the intermolecular annulations of ynamide analogs including ynol ethers and thioalkynes are also discussed, which can provide insights into the reactivity difference caused by the heteroatoms.
酰亚胺是一种独特的炔烃，其碳-碳三键直接连接到带有吸电子基团的氮原子上。炔键被供电子氮原子强烈极化，但吸电子基团可以精细调节其高反应性。因此，酰亚胺具有亲核性和亲电性，它们的化学性质一直是一个活跃的研究领域。过去十年中，酰亚胺的催化分子间环化反应受到了广泛关注，这种反应以区域选择性的方式实现了结构重要的氨基杂环的多样化组装。本综述旨在全面总结这一领域在过渡金属和酸催化方面的进展。此外，还讨论了包括炔醇醚和硫代炔烃在内的酰亚胺类似物的分子间环化反应，这可以深入了解杂原子引起的反应性差异。
