Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200438, P. R. China.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China.
Angew Chem Int Ed Engl. 2019 Oct 7;58(41):14653-14659. doi: 10.1002/anie.201907840. Epub 2019 Sep 5.
A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd-catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example of a highly enantioselective intramolecular cyclization/cross-coupling of olefin-tethered aryl halides with alkyl-, alkenyl- or arylboronic acids, and provides rapid access to a number of chiral compounds, such as dihydrobenzofurans, indolines, chromanes, and indanes bearing a quaternary stereocenter, in good yields with excellent enantioselectivities. The practicality of this reaction was validated in the modification of biologically complex molecules such as peptides, piperitol, CB2 receptor agonists, etc. Moreover, the synthesis of two enantiomers can be easily realized by simple change in the order of the steps in the coupling sequence.
通过钯催化的不对称串联 Heck/Suzuki 偶联反应，实现了未活化烯烃的高对映选择性双官能化。该反应代表了首例高对映选择性的烯丙基芳基卤化物与烷基、烯基或芳基硼酸的分子内环化/交叉偶联反应，为许多手性化合物的快速合成提供了途径，如二氢苯并呋喃、吲哚啉、色满和茚满，它们都带有一个季立体中心，产率高，对映选择性好。该反应的实用性已通过对生物复杂分子如肽、哌啶醇、CB2 受体激动剂等的修饰得到验证。此外，通过简单改变偶联序列中步骤的顺序，很容易实现两种对映异构体的合成。
