Cook Andrea M, Wolf Christian
Department of Chemistry, Georgetown University, Washington, DC 20057, USA.
Tetrahedron Lett. 2015 May 6;56(19):2377-2392. doi: 10.1016/j.tetlet.2015.03.111.
Ynamides consist of a polarized triple bond that is directly attached to a nitrogen atom carrying a sulfonyl, an alkoxycarbonyl, an acyl or another electron withdrawing group. The triple bond polarization renders ynamides broadly useful building blocks with synthetic opportunities that go far beyond traditional alkyne chemistry. The versatile reactivity of ynamides in cycloadditions, cycloisomerizations, regioselective additions with various nucleophiles or electrophiles, ring-closing metathesis, and many other reactions has been investigated in detail during the past decades. A common feature of these methods is that the triple bond is consumed and either cleaved or transformed to a new functionality. The wealth of reports on these ynamide reactions is in stark contrast to the dearth of carbon-carbon bond formations that leave the triple bond of terminal ynamides intact. The recent introduction of effective synthetic methods for the preparation of terminal ynamides has set the stage to fully explore the synthetic potential of this intriguing class of compounds. This digest letter summarizes the most effective routes to terminal ynamides and the current state of selective nucleophilic addition, substitution and coupling reactions, including the first examples of asymmetric synthesis.
烯二酰胺由一个极化的三键组成，该三键直接连接到一个带有磺酰基、烷氧羰基、酰基或另一个吸电子基团的氮原子上。三键极化使烯二酰胺成为具有广泛用途的构建单元，其合成机会远远超出传统炔烃化学。在过去几十年中，人们对烯二酰胺在环加成、环异构化、与各种亲核试剂或亲电试剂的区域选择性加成、关环复分解反应以及许多其他反应中的多功能反应性进行了详细研究。这些方法的一个共同特点是三键被消耗，要么断裂，要么转化为新的官能团。关于这些烯二酰胺反应的大量报道与使末端烯二酰胺的三键保持完整的碳 - 碳键形成的匮乏形成了鲜明对比。最近引入的用于制备末端烯二酰胺的有效合成方法为充分探索这类有趣化合物的合成潜力奠定了基础。这篇综述信函总结了制备末端烯二酰胺的最有效路线以及选择性亲核加成、取代和偶联反应的当前状态，包括不对称合成的首个实例。
