Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and Technology, State Key Laboratory for Conservation and Utilization of Bio-Resources in Yunnan, Yunnan University, Kunming, 650091, China.
Angew Chem Int Ed Engl. 2019 Mar 26;58(14):4710-4713. doi: 10.1002/anie.201901511. Epub 2019 Feb 27.
The first Pd-catalyzed asymmetric allenylic [4+1] cycloaddition was successfully developed. Alternatively, tuning the Pd catalyst switched the reactivity toward an unprecedented [4+3] cycloaddition/cross-coupling. Ligands play a vital role in controlling the reaction pathway, allowing highly selective access to different products from identical substrates. Biological evaluation of the obtained compounds led to the discovery of new antitumor targets. A possible mechanism is proposed, suggesting two interesting catalytic cycles for the cycloaddition with palladium-butadienyls. This study also demonstrated the potential and utility of allenic esters as 1,4-biselectrophiles and C synthons for participating in cycloaddition reactions.
首次发展了钯催化的不对称烯丙基[4+1]环加成反应。另外，通过调节钯催化剂，可以使反应朝着前所未有的[4+3]环加成/交叉偶联反应转变。配体在控制反应途径方面起着至关重要的作用，可以从相同的底物中高度选择性地获得不同的产物。对获得的化合物进行的生物学评价导致了新的抗肿瘤靶标的发现。提出了一种可能的机制，为钯-丁二烯的环加成反应提出了两个有趣的催化循环。该研究还证明了烯丙基酯作为 1,4-双亲电试剂和 C 合成子参与环加成反应的潜力和实用性。
