Huang Chengmi, Wu Dong, Li Yangyang, Yin Guoyin
The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei 430072, People's Republic of China.
J Am Chem Soc. 2023 Aug 30;145(34):18722-18730. doi: 10.1021/jacs.3c05969. Epub 2023 Aug 15.
Selective transformation of alkyne triple bonds to double bonds serves as an efficient platform to construct substituted alkenes. While significant advances have been made in its spatiotemporal regulation, achieving a multicomponent enantioselective reaction that requires multifaceted selectivity issues to be overcome is still uncommon. Here, we report an unprecedented asymmetric -stereoselective borylcarbofunctionalization of terminal alkynes by nickel catalysis. The utilization of an inexpensive chiral diamine ligand enables the three-component cross-coupling of terminal alkynes, a diboron reagent, and prochiral alkyl electrophiles with high levels of regio-, stereo-, and enantioselectivities. This reaction provides an efficient protocol to access enantioenriched alkenyl esters bearing an α-stereogenic center, is remarkably practical, and has a broad scope and an outstanding functional group compatibility. In addition, the value of this method has been highlighted in a diversity of follow-up stereoretentive derivatizations and the stereoselective concise synthesis of complex drug molecules.
将炔烃三键选择性转化为双键是构建取代烯烃的有效平台。尽管在其时空调控方面已取得重大进展，但实现需要克服多方面选择性问题的多组分对映选择性反应仍然并不常见。在此，我们报道了一种前所未有的镍催化末端炔烃的不对称 -立体选择性硼基碳官能化反应。使用廉价的手性二胺配体可实现末端炔烃、二硼试剂和前手性烷基亲电试剂的三组分交叉偶联，具有高水平的区域选择性、立体选择性和对映选择性。该反应提供了一种有效的方法来获得带有α-立体中心的对映体富集的烯基酯，非常实用，具有广泛的底物范围和出色的官能团兼容性。此外，该方法的价值在多种后续的立体保持衍生化反应以及复杂药物分子的立体选择性简洁合成中得到了凸显。
