Chen Xiao-Bing, Padín Damián, Stindt Charlotte N, Feringa Ben L
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
Angew Chem Int Ed Engl. 2023 Aug 14;62(33):e202307450. doi: 10.1002/anie.202307450. Epub 2023 Jul 6.
P-stereogenic compounds are widely used as ligands in asymmetric catalysis and are present in a myriad of bioactive compounds and pharmaceuticals. Yet, their stereocontrolled preparation remains challenging. Herein, we report a novel strategy towards versatile chiral-at-P alkenylphosphonamidates through a one-pot Ni-catalyzed C-P coupling/diastereoselective hydrolysis of readily available phosphoramidites and alkenyl halides. Remarkably, a chemo- and diastereodivergent behavior was observed upon subtle changes in the reaction conditions. Additionally, selective derivatizations of chiral alkenylphosphonamidates demonstrate their versatility as building blocks for the synthesis of structurally diverse P-stereogenic compounds.
P-手性化合物在不对称催化中广泛用作配体，并且存在于众多生物活性化合物和药物中。然而，它们的立体控制制备仍然具有挑战性。在此，我们报道了一种通过一锅法镍催化易得的亚磷酰胺酯和烯基卤化物进行C-P偶联/非对映选择性水解来制备通用的P-手性烯基膦酰胺酯的新策略。值得注意的是，在反应条件发生细微变化时观察到了化学和非对映发散行为。此外，手性烯基膦酰胺酯的选择性衍生化证明了它们作为合成结构多样的P-手性化合物的砌块的通用性。
