DeRatt Lindsey G, Pappoppula Mukesh, Aponick Aaron
Florida Center for Heterocyclic Compounds & Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, FL, 32607, USA.
Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8416-8420. doi: 10.1002/anie.201902405. Epub 2019 May 10.
The first catalytic enantioselective alkynylation of chromones is reported. In this process, chromones are silylated to form silyloxybenzopyrylium ions that lead to silyl enol ethers after Cu-catalyzed alkyne addition using StackPhos as a ligand. The outcome of the reaction is impacted by distal ligand substituents with differing electronic character and it was found that successful reactions could be achieved with different ligand congeners by using different solvents. This sequence enables access to different products by protonation or further functionalization, thus increasing complexity in a divergent manner. The transformation is high yielding over a broad scope to provide a variety of useful chromanones in high enantioselectivity.
报道了首例色酮的催化对映选择性炔基化反应。在此过程中，色酮被硅烷化形成硅氧基苯并吡喃鎓离子，在使用StackPhos作为配体的情况下，经铜催化的炔烃加成反应后生成烯醇硅醚。反应结果受具有不同电子性质的远端配体取代基影响，并且发现通过使用不同的溶剂，不同的配体类似物可实现成功反应。该反应序列通过质子化或进一步官能化能够得到不同的产物，从而以发散的方式增加了化合物的复杂性。该转化反应在广泛的底物范围内具有高产率，能够以高对映选择性提供多种有用的色满酮。
